CN118406287B - Modified calcium carbonate special for polyvinyl chloride composite material and application thereof - Google Patents
Modified calcium carbonate special for polyvinyl chloride composite material and application thereof Download PDFInfo
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- CN118406287B CN118406287B CN202410399301.XA CN202410399301A CN118406287B CN 118406287 B CN118406287 B CN 118406287B CN 202410399301 A CN202410399301 A CN 202410399301A CN 118406287 B CN118406287 B CN 118406287B
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- Prior art keywords
- calcium carbonate
- polyvinyl chloride
- modified
- stabilizer
- modified layer
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 515
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 147
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 146
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 219
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000003381 stabilizer Substances 0.000 claims abstract description 50
- 238000012545 processing Methods 0.000 claims abstract description 49
- 239000003607 modifier Substances 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000000314 lubricant Substances 0.000 claims abstract description 26
- 239000004014 plasticizer Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 22
- -1 pentaerythritol ester Chemical class 0.000 claims description 55
- 229910019142 PO4 Inorganic materials 0.000 claims description 48
- 239000010452 phosphate Substances 0.000 claims description 48
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 235000019198 oils Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000006084 composite stabilizer Substances 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001463 antimony compounds Chemical class 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 2
- BKMAEERFCKIKJR-UHFFFAOYSA-N 2-tridecoxycarbonylbenzoic acid Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(O)=O BKMAEERFCKIKJR-UHFFFAOYSA-N 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- GQIDSVPVVYHXAP-UHFFFAOYSA-N dihexyl decanedioate Chemical compound CCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC GQIDSVPVVYHXAP-UHFFFAOYSA-N 0.000 claims description 2
- OJXOOFXUHZAXLO-UHFFFAOYSA-M magnesium;1-bromo-3-methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC(Br)=C1 OJXOOFXUHZAXLO-UHFFFAOYSA-M 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 2
- ZGHZSTWONPNWHV-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC1CO1 ZGHZSTWONPNWHV-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- 230000000704 physical effect Effects 0.000 abstract description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 209
- 239000010410 layer Substances 0.000 description 94
- 230000000694 effects Effects 0.000 description 32
- 239000000463 material Substances 0.000 description 26
- 238000012986 modification Methods 0.000 description 25
- 230000004048 modification Effects 0.000 description 25
- 239000000047 product Substances 0.000 description 23
- 239000007822 coupling agent Substances 0.000 description 21
- 230000002829 reductive effect Effects 0.000 description 20
- 239000002245 particle Substances 0.000 description 14
- 238000004873 anchoring Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 230000004913 activation Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000011049 filling Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000007614 solvation Methods 0.000 description 4
- 239000004566 building material Substances 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000051 modifying effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses special modified calcium carbonate for a polyvinyl chloride composite material, which comprises the following components in parts by weight: 100.1 to 103 parts of coated calcium carbonate, 1 to 3 parts of stabilizer, 1 to 5 parts of plasticizer, 0.5 to 2 parts of processing modifier and 1 to 3 parts of lubricant; the coated calcium carbonate comprises calcium carbonate and a modified layer coated on the surface of the calcium carbonate, wherein the modified layer comprises a first modified layer and a second modified layer; the preparation raw materials of the first modified layer comprise high-molecular polymer hyperdispersant, and the preparation raw materials of the second modified layer comprise phosphate compounds. The modified calcium carbonate is prepared by coating calcium carbonate with a specific structure and combining with a processing modifier and the like, is specially used in a polyvinyl chloride composite material, and can improve the compatibility of the calcium carbonate and the polyvinyl chloride, improve the processing fluidity, the physical properties and the like of the polyvinyl chloride.
Description
Technical Field
The invention relates to modified calcium carbonate and a preparation method and application thereof, in particular to modified calcium carbonate special for polyvinyl chloride and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is a versatile plastic with excellent overall properties, with yields inferior to Polyethylene (PE). The plastic has the advantages of flame retardance, corrosion resistance, wear resistance, oil resistance, good insulativity, good light transmittance and the like, and the price is one of five general plastics with the lowest price, so the plastic has wide raw material sources, is widely applied in various fields, particularly the field of building materials, is manufactured into chemical building materials such as various pipes, plates, sectional materials and the like, replaces steel materials and wood in a large number, and has the advantages of saving energy, building materials, protecting ecology, improving living environment, improving building functions and quality, reducing self weight of the building, being convenient to construct and the like. However, PVC has some defects due to its molecular structure, firstly, the molecular structure contains allyl chloride and tertiary chloride, and after being heated, dehydrochlorination reaction occurs to promote degradation, resulting in poor thermal stability and easy decomposition; secondly, as the molecular chain contains a large number of C-Cl bonds and has high polarity, the intermolecular acting force is strong, the material strength is high, the low-temperature brittleness and the toughness are poor, and especially the notch impact strength is more sensitive; thirdly, the viscosity of the pure PVC resin is high, so that the processing fluidity is poor, the processing temperature window is narrow because the temperature is increased and the pure PVC resin is decomposed. PVC application is greatly limited due to the above drawbacks. Therefore, the polyvinyl chloride needs to be modified to expand the application field of the polyvinyl chloride, so that the problems of toughness, thermal stability, easy aging, difficult processing and the like of the polyvinyl chloride are improved, the polyvinyl chloride is endowed with new performance, and the application field of the polyvinyl chloride is expanded.
The toughening modification of PVC is generally divided into two types, namely chemical modification and physical modification. The cost of chemical modification is high, the process is complex, the equipment requirement is strict, and the application is limited. At present, the blending modification is mainly carried out by adopting a physical method internationally. The blending modification is mainly organic modification and inorganic modification, and the organic modification is generally to add a high-molecular elastic material and a plasticizer into PVC, but the method improves the toughness, reduces the rigidity, the strength and the dimensional stability of the material, reduces the heat resistance and has high cost; in addition, the plasticizer contains dioxin, which is harmful to human bodies. Therefore, most of the inorganic materials at home and abroad are modified, and the common inorganic materials mainly comprise inorganic powder such as calcium carbonate, talcum powder, diatomite, titanium dioxide, wood powder and the like. At present, the most used is calcium carbonate, because the calcium carbonate can improve the heat resistance, the wear resistance, the toughness, the dimensional stability, the rigidity and the processability of the product, and meanwhile, the raw material source is wide, the price is low, the cost of the product can be reduced, and the calcium carbonate is the inorganic filling material with the largest using amount and the widest at home and abroad.
However, there are two major drawbacks to using calcium carbonate directly for modifying polyvinyl chloride: (1) Intermolecular forces, electrostatic interactions, hydrogen bonds, oxygen bridges, etc. can cause agglomeration of calcium carbonate powder; (2) The calcium carbonate surface has strong hydrophilicity and is in strong alkaline hydroxyl, so that the affinity between the calcium carbonate and a polymer is poor, an aggregate is easy to form, the dispersibility in the polymer is poor, defects exist between two material interfaces, the mechanical properties such as tensile strength, impact strength and elongation at break of a polyvinyl chloride product are reduced, and the defects are more obvious along with the increase of the filling quantity of the calcium carbonate. In addition, because the calcium carbonate has small particle size and high surface energy, is in a thermodynamically unstable state and is extremely easy to agglomerate, the calcium carbonate is difficult to uniformly disperse in a (PVC) matrix, so that the structure of the composite material has great defects, and the filling quantity is low. Therefore, to improve the wettability of calcium carbonate in polyvinyl chloride, reduce the cohesive force between particles, improve the dispersibility, improve the surface activity of calcium carbonate, improve the acid resistance, enhance the uniform dispersibility and hydrophobic lipophilicity of the calcium carbonate in PVC composite material, improve the comprehensive performance of the PVC/CaCO 3 composite material, improve the filling amount of the calcium carbonate in the composite material, the surface modification of the calcium carbonate is needed, the surface energy of the calcium carbonate is changed, and the compatibility with the polyvinyl chloride is improved.
The surface modification of calcium carbonate is to adsorb or react the surface modifier onto the surface of calcium carbonate to form coating film to activate the surface and to possess active polymer radical, so as to improve the surface performance of calcium carbonate and the compatibility of calcium carbonate with polymer. Along with the continuous development of inorganic powder particle refinement technology and surface modification technology, calcium carbonate is applied to polyvinyl chloride filling modification technology more and more, but the currently marketed coated calcium carbonate can only be used for part of low-end products, has a plurality of problems in the use of products such as high-end electronic appliances, electric power and communication, and the like, firstly has low filling quantity, generally only 15-20%, secondly has poor heat stability and low-temperature brittleness, and mainly has poor surface modification effect, so that the compatibility of the coated calcium carbonate with polyvinyl chloride is poor. At present, the surface modification method of calcium carbonate at home and abroad mainly adopts a coupling agent to carry out surface modification treatment on the calcium carbonate, and the commonly used coupling agent mainly comprises a titanate coupling agent, an aluminate coupling agent and a silane coupling agent. The whiteness of the modified product is affected by the brown color of the titanate coupling agent, the price is high, the titanate coupling agent (phthalate) possibly endangers the health of human bodies (causing liver cancer), and the developed world has established strict regulations on the content of titanate in products such as pacifiers, toys and the like. Thus, in recent years the use of titanates for the surface modification of calcium carbonate has been a tendency to shrink; the silane coupling agent is the earliest coupling agent, but most of the silane coupling agents have weak surface binding force with CaCO 3, and is more effective multi-component silane coupling agents, which can enable the CaCO 3 powder to be subjected to surface silanization, but the cost is very high, and the silane coupling agent is liquid and complex in use and operation, so that the silane coupling agent is not suitable for mass production and use; The aluminate coupling agent is a coupling agent developed in recent years, main raw materials for producing the aluminate coupling agent are mostly organic acids (such as oleic acid, stearic acid, paraffin and the like), nonpolar long-chain alkane is derived from different organic acids, so that the relative molecular mass of the produced aluminate lipophilic group is smaller, the lipophilic molecular weight is generally smaller than 1000, the aluminate coupling agent cannot form effective winding with molecular bonds of high polymer materials, the mechanical property of the composite material is improved, the price and the performance difference are also large, and the stability is very poor. More importantly, when the coupling agents are combined with polyvinyl chloride containing a large amount of C-C1 bonds, having very high polarity, strong intermolecular action and strong hydrophobicity, the intermolecular force between the systems is relatively poor, the compatibility is poor, and especially when in hot processing, the coupling agents are quickly decomposed and gasified under the action of thermal dehydrochlorination reaction of the polyvinyl chloride, are discharged from materials and discharged through the exhaust holes of an extruder, so that the activation effect is lost, and serious pollution is caused to the production environment. Meanwhile, because of the poor thermal stability of the coupling agents, active groups which can react with each other or intertwine with the polymer on the surface of the calcium carbonate are less and less along with the increase of the processing temperature, the dosage of the coupling agents can be greatly increased in the actual production in order to maintain the basically normal production, especially when the coupling agents are processed with the polyvinyl chloride/calcium carbonate composite modified material containing a large amount of C-CI polar bonds, HCI molecules are more easily removed from the polyvinyl chloride, the unsaturated bonds are introduced into macromolecular chains to form thermal decomposition, the accelerated decomposition of micromolecular compounds in the coupling agents into gas discharged materials is promoted, the dispersibility and the fluidity of the materials are poor, The processing is difficult, the materials can generate strong friction heat with the machine barrel and the screw rod, the temperature of the materials in the machine barrel is rapidly increased, the decomposition of polyvinyl chloride with strong heat sensitivity is aggravated, and as the temperature of production equipment is continuously increased, the active groups on the surface of the coated calcium carbonate can react with the active groups of the polyvinyl chloride more and less, so that the interface compatibility of the polyvinyl chloride/calcium carbonate modified composite material is poor, and the material performance is also greatly reduced.
Therefore, when the coupling agent is used for modifying calcium carbonate, the activated calcium carbonate finally obtained has the biggest problems of not high temperature resistance and easy decomposition when being applied to polyvinyl chloride processing, the filling quantity can not be improved, the higher the filling quantity is, the more the performance is reduced, the poor thermal stability is generally poor, the problems of poor processing fluidity, low toughness, low strength and other performances of the polyvinyl chloride can not be effectively solved, the use requirement of high-end products can not be met, and the method is not well applicable to the preparation of the polyvinyl chloride composite material.
Disclosure of Invention
The invention aims to solve the problems of poor thermal stability, easy formation of agglomerates and the like of the modified calcium carbonate used in the polyvinyl chloride, and provides the modified calcium carbonate which has good thermal stability, can be uniformly dispersed in a polyvinyl chloride matrix, has good compatibility with the polyvinyl chloride matrix, can obviously improve the comprehensive performance of the polyvinyl chloride and reduce the production cost of the polyvinyl chloride. Meanwhile, the invention also provides a preparation method of the modified calcium carbonate and application of the modified calcium carbonate in the polyvinyl chloride composite material.
In order to achieve the above purpose, in a first aspect, the invention provides a modified calcium carbonate special for polyvinyl chloride composite material, comprising the following components in parts by weight: 100.1 to 103 parts of coated calcium carbonate, 1 to 3 parts of stabilizer, 1 to 5 parts of plasticizer, 0.5 to 2 parts of processing modifier and 1 to 3 parts of lubricant;
the coated calcium carbonate comprises calcium carbonate and a modified layer coated on the surface of the calcium carbonate, and the mass ratio of the calcium carbonate to the modified layer is 100: (0.1-3);
the modified layer comprises a first modified layer coated on the surface of the calcium carbonate and a second modified layer coated on the outer surface of the first modified layer;
the preparation raw materials of the first modified layer comprise high-molecular polymer hyperdispersant which is a mixture of polyester hyperdispersant, polyacrylate hyperdispersant and polyolefin hyperdispersant;
the preparation raw materials of the second modified layer comprise phosphate compounds, and the phosphate compounds are a mixture of fatty alcohol polyoxyethylene ether phosphate, dodecyl phosphate and castor oil phosphate.
The inventor researches and obtains special modified calcium carbonate aiming at polyvinyl chloride according to the structure and performance characteristics of the polyvinyl chloride, wherein the modified calcium carbonate comprises coated calcium carbonate with a specific structure, a stabilizer, a plasticizer, a processing modifier and a lubricant, and the special modified calcium carbonate is directly added into the polyvinyl chloride according to a certain proportion in the preparation of a polyvinyl chloride composite material.
In the modified calcium carbonate special for polyvinyl chloride, the coated calcium carbonate is obtained by repeated experiments and researches of the inventor, and the inventor finds that when the modified activation is carried out on the calcium carbonate special for polyvinyl chloride, the conventional coupling agents such as titanate coupling agent, aluminate coupling agent, silane coupling agent and the like can not be adopted for modification. The application innovatively adopts a double-layer composite activation modification technology to carry out surface modification coating on calcium carbonate, wherein a first modification layer adopts a specific selected high polymer hyperdispersant, a second modification layer selects a specific phosphate compound mixture, and the modified calcium carbonate can be attached to the structural and performance defects of a polyvinyl chloride material by combining the specific amount ratio with the combination of the selected substances such as a stabilizer, a processing modifier and the like through the cooperation of two layers, so that the modified calcium carbonate has good compatibility and reinforcing effects with the polyvinyl chloride.
Specifically, the special modified calcium carbonate for the polyvinyl chloride composite material comprises specific parts by weight of coated calcium carbonate, a stabilizer, a plasticizer, a processing modifier and a lubricant, wherein the coated calcium carbonate comprises calcium carbonate and a modified layer coated on the surface of the calcium carbonate, and the modified layer comprises a first modified layer and a second modified layer, namely the coated calcium carbonate is provided with a double-layer coating layer. The first modified layer is prepared from a high molecular polymer hyperdispersant which is selected specifically, wherein the high molecular polymer hyperdispersant contains an anchoring group and a solvation chain, the anchoring group can be tightly adsorbed on the surface of calcium carbonate in a single-point or multi-point anchoring mode through the actions of ionic bonds, hydrogen bonds and the like, and the adsorption type is irreversible, so that the first modified layer is difficult to desorb on the surface of the calcium carbonate, and a firm coating effect is formed. The solvated chain can further form a protective layer with a certain thickness on the surface of the calcium carbonate, when the calcium carbonate particles are close to each other, the calcium carbonate with the first modified layer is difficult to form compact aggregates or floccules due to the space barrier effect of the protective layer, so that the coated calcium carbonate has good dispersibility when used for polyvinyl chloride. Meanwhile, the high-molecular polymer hyper-dispersant has high temperature resistance, stable chemical performance, no precipitation and certain reactivity, and can capture free radicals or polar bonds of a polymer system, thereby generating better chemical coupling effect and improving the mechanical properties of the composite material. More importantly, the first modified layer is prepared from three different types of hyperdispersant mixtures, wherein in the mixture formed by the three different types of hyperdispersants, anchoring groups and macromolecule solvation chain segments in molecular configurations of the three different types of hyperdispersant mixtures have different molecular configurations such as single-point connection, block connection, comb connection and the like, and the hyperdispersant mixtures with multiple molecular configurations can form a firmer adsorption effect on the surface of calcium carbonate on one hand and can be tightly attached to the second modified layer on the other hand. The second modified layer is prepared by adopting a phosphate compound, compared with the high-molecular polymer hyperdispersant, the phosphate compound has low price, large production quantity, multiple varieties and easy acquisition, the second layer is prepared by selecting the phosphate compound with specific functions through molecular design, the second modified layer can be firmly combined with the first modified layer, the calcium carbonate can be further subjected to surface activation modification, the phosphate compound not only has the functions of obviously improving the processability and mechanical properties of the calcium carbonate and effectively improving the corrosion resistance and flame retardance of the material, but also has a plasticizing function on polyvinyl chloride, and the using amount of a plasticizer can be effectively reduced.
In the modified calcium carbonate, the stabilizer can inhibit or prevent resin degradation, has an antioxidation effect, absorbs ultraviolet rays or shields the damage of ultraviolet rays to the resin, and prolongs the service life of the product. The plasticizer can be classified into cold-resistant plasticizers, high-temperature-resistant plasticizers, heat-resistant and light-resistant plasticizers, flame-retardant plasticizers, nontoxic plasticizers, antibacterial plasticizers and the like according to different performances, and different plasticizers can be used according to different technical requirements of products. The processing modifier is mainly used for improving the processing fluidity and the melt strength of the calcium carbonate modified polymer composite material, improving the low-temperature brittleness and the flame retardance of products and improving the tensile strength, the impact strength and the elongation at break. The lubricant can improve the processing fluidity of polyvinyl chloride, reduce the friction force of materials and processing equipment, and avoid the decomposition of the materials caused by the increase of the processing temperature. The coated calcium carbonate with the specific structure can improve the rigidity of polyvinyl chloride, the dimensional stability and the low temperature resistance and the like. The composition of the components such as the coated calcium carbonate with the specific structure, the stabilizer and the like, the selection and the quantitative ratio of each component can be fit with the structure and the performance characteristics of the polyvinyl chloride, and when the modified calcium carbonate is applied to the preparation of the polyvinyl chloride composite material from the polyvinyl chloride, the performance defect of the polyvinyl chloride at present can be effectively solved, and the comprehensive performance of the polyvinyl chloride is obviously improved.
The formula of the modified calcium carbonate is developed by combining the structure and performance characteristics of polyvinyl chloride according to the results of repeated exploration tests aiming at the problems existing in the preparation process of the polyvinyl chloride composite material, is special for the application of the polyvinyl chloride composite material, and cannot be well applied to polymer plastics with other components.
The quality ratio of the coated calcium carbonate to the modified layer adopted in the application has direct influence on the performance achieved after the coated calcium carbonate (activated) is added into the polyvinyl chloride, when the quality of the modified layer is too high, the coated layer on the surface of the calcium carbonate is too thick, the anchoring force is reduced, part of the high polymer hyperdispersant cannot effectively anchor the surface of the calcium carbonate, the coated protective layer is unstable, delamination is easy to occur, and the effective combination of the coated calcium carbonate and the polyvinyl chloride is reduced. When the quality of the modified layer is too low, the modified layer can not completely coat the calcium carbonate, and the modified layer still has the problems of easy agglomeration, poor compatibility with a polyvinyl chloride matrix and incapability of adding a large amount after the polyvinyl chloride is added. The inventor found through experiments that when the mass ratio of the calcium carbonate to the modified layer is 100: (0.1-3), the modified layer has better coating on calcium carbonate, and the prepared coated calcium carbonate can achieve better comprehensive performance when used for polyvinyl chloride.
More preferably, the mass ratio of the calcium carbonate to the modified layer is 100: (1-3), for example, include but are not limited to 100:1.5, 100:2, etc. When the mass ratio of the calcium carbonate to the modified layer is 100: (1-3) the modified layer has a more sufficient coating activation effect on calcium carbonate without causing adverse effects caused by an excessive amount of the modified layer.
The calcium carbonate adopted in the invention is common calcium carbonate in the prior art, and can be directly purchased in the market or prepared by adopting a known conventional method. The calcium carbonate is preferably calcium carbonate with the whiteness of 96-99.5%, caCO 3 content of up to 99.5%, particle size of 800-2500 meshes and uniform particle size distribution.
Preferably, in the modified layer coated with calcium carbonate, the mass ratio of the first modified layer to the second modified layer is 1: (1-3). Of the modified layers, the first modified layer and the second modified layer are as follows: when the mass ratio of (1-3) is distributed, a sufficient amount of high polymer hyperdispersant exists in the first modified layer, solvated chains can form a protective layer with a certain thickness on the surface of calcium carbonate, and anchoring groups can be firmly adsorbed on the surface of the calcium carbonate in a single-point or multi-point anchoring manner, so that the first modified layer has sufficient adsorption force on the surface of the calcium carbonate, desorption cannot exist when the first modified layer is used for polyvinyl chloride later, and the protective layer with a proper thickness can make the calcium carbonate particles difficult to form compact agglomerates and floccules due to the space barrier effect of the protective layer when the calcium carbonate particles are close to each other, thereby endowing the coated calcium carbonate with good dispersibility. Meanwhile, due to the design of the first modified layer and the second modified layer in the mass ratio, the cost of the coated calcium carbonate is effectively reduced on the basis of ensuring that the modified calcium carbonate has good heat stability, dispersibility and other comprehensive properties.
Preferably, in the high-molecular polymer hyperdispersant, the high-molecular polymer hyperdispersant is a mixture of products of which the types are LD-1060, LD-1651 and LD-300P. More preferably, in the high-molecular polymer hyperdispersant, the mass ratio of each component is LD-1060: (LD-1651+ld-300P) = (2 to 5): 1. the LD-1060, LD-1651 and LD-300P were all purchased from Dada resin Co., inc. in Yangzhou.
The inventor selects high polymer dispersants from different manufacturers for research, and through repeated experimental research, the inventor finds that when only three high polymer hyperdispersants of which the product types are LD-1060, LD-1651 and LD-300P are respectively adopted by the product types of the Daida resin limited company, yangzhou, the modifying and activating effects of the first modified layer on the surface of calcium carbonate are better, the anchoring and adsorbing effects of the first modified layer on the surface of calcium carbonate are firmest, and meanwhile, the matching effect of the first modified layer and the second modified layer is excellent. Meanwhile, the inventor researches and tests the influence of the mass ratio of three types of high polymer hyperdispersants on the performance of the coated calcium carbonate, and finally discovers that the mass ratio of the three types of high polymer hyperdispersants is LD-1060: (LD-1651+ld-300P) = (2 to 5): and 1, the finally obtained coated calcium carbonate can obtain better performance after being added with polyvinyl chloride.
Preferably, the mass ratio of the LD-1651 to the LD-300P is (1-2): (1-2). In the high molecular polymer hyperdispersant, LD-1651 and LD-300P need to be added in proper amounts to form mutual coordination through anchoring groups and surface molecular structures of different types of hyperdispersants.
More preferably, in the high-molecular polymer hyperdispersant, the mass ratio of each component is LD-1060: (LD-1651+ld-300P) = (2 to 5): 1, and the mass ratio of the LD-1651 to the LD-300P is 1:1.
Preferably, the mass ratio of each component in the phosphate compound is fatty alcohol polyoxyethylene ether phosphate: dodecyl phosphate: castor oil phosphate = 4: (1-2): (1-3). More preferably, the mass ratio of each component in the phosphate compound is fatty alcohol polyoxyethylene ether phosphate: dodecyl phosphate: castor oil phosphate = 4:2:2.
Compared with a high molecular polymer hyperdispersant, the phosphate compound has the advantages of low price, multiple varieties, easy obtainment and the like, the phosphate compound is adopted to carry out secondary surface activation modification on the calcium carbonate coated with the first modified layer, the phosphate compound belongs to an anionic surfactant, calcium phosphate is mainly formed by the combination reaction of phosphate (ROPO 3H2) and Ca 2+ on the surface of the calcium carbonate to deposit or coat the calcium phosphate on the surface of the calcium carbonate particles, the R groups of the phosphate on the surface of CaCO 3 are arranged outwards, so that the lipophilicity of the modified calcium carbonate is enhanced, the surface performance of the calcium carbonate powder is changed, the compatibility with polyvinyl chloride is improved, and the mechanical property and the processing property of the polyvinyl chloride/calcium carbonate composite material are further improved. Meanwhile, the flame retardance and corrosion resistance of the product are improved, the phosphate compound has good plasticizing effect on polyvinyl chloride, and the dosage of the plasticizer can be reduced. The inventor discovers that in the second modified layer of the outermost layer of the coated calcium carbonate, the selection of the phosphate compound has direct influence on the compatibility, flame retardance, corrosion resistance and the like of the modified calcium carbonate prepared by mixing the coated calcium carbonate with other components in polyvinyl chloride, and the repeated experiments in the research show that when the second modified layer of the outermost layer of the coated calcium carbonate adopts the following components in mass ratio: fatty alcohol polyoxyethylene ether phosphate: dodecyl phosphate: castor oil phosphate = 4: (1-2): when the mixture of (1-3) is mixed with other components, the coated calcium carbonate formed by coating the calcium carbonate with the phosphate compound has better compatibility with polyvinyl chloride and obviously improves the comprehensive performance of the polyvinyl chloride composite material. When fatty alcohol polyoxyethylene ether phosphate: dodecyl phosphate: castor oil phosphate = 4:2:2, the effect achieved by the mutual matching of the components is more remarkable.
Preferably, the stabilizer is at least one of a tin compound stabilizer, a calcium-zinc compound stabilizer, an antimony compound stabilizer, and a rare earth compound stabilizer. More preferably, in the stabilizer, the tin-based composite stabilizer is at least one selected from DBTL, DOTL, DMTFG, DBTM, DOTTG; the calcium-zinc compound stabilizer is at least one selected from ST-901B, ST-381 and ST-905; the antimony compound stabilizer is at least one selected from STH-1 and STH-II; the rare earth compound stabilizer is at least one selected from stearic acid rare earth stabilizer, fatty acid rare earth stabilizer, lauric acid rare earth stabilizer, salicylic acid rare earth stabilizer, citric acid rare earth stabilizer, caprylic acid rare earth stabilizer, oleic acid rare earth stabilizer, phthalic acid monoester rare earth stabilizer, thiolate rare earth stabilizer and thiol ester based rare earth stabilizer.
Preferably, the plasticizer is at least one of dihexyl sebacate, dihexyl adipate, trioctyl phosphate, tridecyl phthalate, pentaerythritol ester, trimethyl benzoate, epoxystearyl ester, epoxyoctyl ester, epoxysoybean oil trimethyl phosphate, tri-n-butyl citrate and phthalate.
Preferably, the processing modifier is at least one of acrylic ester copolymer, methyl methacrylate-butadiene-styrene copolymer and chlorinated polyethylene. More preferably, the acrylic copolymer in the processing modifier is at least one selected from the group consisting of ACR-201, ACR-301, ACR-401, ACR-501, ACR-601, P-5335, and P-551; the methyl methacrylate-butadiene-styrene copolymer is selected from at least one of B-564, B-625, B-621, MR-160, MR-363, PA-20 and M-61; the chlorinated polyethylene is selected from at least one of CPE130A, CPE, 135A, CPE, 135B, CPE B.
The processing modifier can improve the processing fluidity and the melt strength of the calcium carbonate modified polymer composite material, improve the low-temperature brittleness and the flame retardance of products, and improve the tensile strength, the impact strength and the elongation at break. The inventors have also found in experiments that when the processing modifier is a mixture of ACR-201, ACR-401 and B-564 in the following mass ratio: (ACR-201+acr-401): b-564= (1-5): 1, the processing modifier can be well matched with a high polymer hyperdispersant in the coated calcium carbonate, and when the processing modifier and the high polymer hyperdispersant are added into the polyvinyl chloride, the compatibility between the modified calcium carbonate and the polyvinyl chloride can be further improved due to the structural characteristics of polar high polymers and the mutual matching action of the three substances, and the impact strength and the tensile strength of the prepared polyvinyl chloride composite material are also obviously improved. In the processing modifier, the mass ratio of ACR-201 to ACR-401 is preferably 1:1, and the ACR-201 and ACR-401 have different performance characteristics, so that when the ACR-201 and the ACR-401 are added in equal amounts to be mixed with B-564 to be used as the processing modifier, the compatibility between modified calcium carbonate and polyvinyl chloride can be remarkably improved, and the impact strength and the tensile strength of the polyvinyl chloride composite material can be better improved.
More preferably, the processing modifier is a mixture of ACR-201, ACR-401 and B-564 in the following mass ratio: (ACR-201+acr-401): b-564=4: 1, and the mass ratio of ACR-201 to ACR-401 is 1:1.
Preferably, the lubricant is at least one of a fatty acid-based lubricant, a fatty acid amide-based lubricant, and a hydrocarbon-based lubricant. More preferably, the fatty acid-based lubricant is stearic acid; the fatty acid amide lubricant is at least one selected from oleamide, stearic acid amide, ethylene bis-stearamide and ethylene bis-stearamide; the hydrocarbon lubricant is at least one selected from paraffin wax, polyethylene wax, low molecular polypropylene wax and chlorinated polyethylene wax.
In a second aspect, the invention provides a method for preparing the modified calcium carbonate special for the polyvinyl chloride composite material, which comprises the following steps:
(1) Adding calcium carbonate into a high-speed stirrer, stirring and drying until the water content is less than or equal to 0.2wt%;
(2) Diluting the high molecular polymer hyperdispersant with white oil, adding the white oil into a high-speed stirrer in the step (1) for high-speed stirring, keeping the temperature at 80-125 ℃ and stirring for 5-10 minutes to obtain calcium carbonate with the surface coated with a first modified layer;
(3) Adding the phosphate compound into the high-speed stirrer in the step (1), keeping the temperature at 80-125 ℃, and stirring for 5-10 minutes to obtain coated calcium carbonate;
(4) Slowly adding the stabilizer into the high-speed stirrer in the step (1) and keeping high-speed stirring for 5-10 minutes at the temperature of 80-125 ℃;
(5) Adding the plasticizer, the processing modifier and the lubricant into the high-speed stirrer in the step (1), stirring at a high speed for 5-10 minutes at 80-125 ℃, and then cooling to 35-50 ℃ to obtain the modified calcium carbonate.
According to the preparation method of the modified calcium carbonate special for the polyvinyl chloride composite material, coated calcium carbonate is firstly needed to be prepared, in the preparation process of the coated calcium carbonate, the calcium carbonate is firstly dried, the water content of the dried calcium carbonate is required to be strictly controlled to be less than or equal to 0.2wt%, and if the water content is too high, the mechanical property of the material is reduced, so that the phenomena of rough surface, bubbles, scorching, decomposition and the like of a product can occur. And then stirring the calcium carbonate dried to the water content required by the high-molecular polymer hyperdispersant at a high speed, and keeping stirring for 5-10 minutes at 80-125 ℃, wherein if the water content of the calcium carbonate is too low, the calcium carbonate cannot be gasified and volatilized, and if the temperature is too high, the auxiliary agent is chemically changed to influence the processing fluidity and mechanical properties of the material. And (3) stirring the two materials at a high speed to obtain the calcium carbonate with the surface coated with the first modified layer. And finally, adding the phosphate compound into a high-speed stirrer, stirring for 5-10 minutes at 80-125 ℃ together with the calcium carbonate coated with the first modified layer, wherein the phosphate compound is further coated on the outer surface of the first modified layer in the stirring process, and the performance characteristics of the phosphate compound are utilized to obviously improve the processability, mechanical properties, corrosion resistance and flame retardance of the coated calcium carbonate applied to polyvinyl chloride, and meanwhile, the dosage of the plasticizer in the polyvinyl chloride can be effectively reduced.
In the preparation method of the modified calcium carbonate special for the polyvinyl chloride composite material, in the step (1), the calcium carbonate can be dried by a method known in the prior art, for example, the calcium carbonate can be placed into a high-speed stirrer to be stirred at a high speed at a temperature of between 80 and 125 ℃ until the water content reaches below 0.2 weight percent.
In the preparation method of the special modified calcium carbonate for the polyvinyl chloride composite material, the white oil added in the step (2) is mainly used for diluting the high-molecular polymer hyperdispersant, so that the high-molecular polymer hyperdispersant is better dispersed and uniformly coated on the surface of the calcium carbonate to form a first modified layer. The addition amount of the white oil is 1 to 5 times of the weight of the high molecular polymer hyper-dispersant.
The preparation method of the special modified calcium carbonate for the polyvinyl chloride composite material comprises the steps of firstly drying the calcium carbonate until the water content is less than or equal to 0.2wt%, generally drying in a high-speed stirrer, and then coating a high-molecular polymer hyper-dispersant and a phosphate compound in sequence to obtain coated calcium carbonate; then stirring the stabilizer and the coated calcium carbonate at a high speed in a high-speed stirrer under a specific temperature range, finally adding the plasticizer, the processing modifier and the lubricant, stirring at a high speed for 5-10 minutes at 80-125 ℃, and cooling to 35-50 ℃. Firstly, the stabilizer and the coated calcium carbonate are fully mixed, and the fully mixing of the stabilizer and the coated calcium carbonate can improve the stability of the coated calcium carbonate. Finally, adding auxiliary agents such as plasticizer and the like for mixing, mixing all the raw materials at the specific temperature, and stirring at a high speed, wherein if the temperature of the high-speed stirring is too high, the lubricant, the processing modifier and the like are easy to decompose and denature, and if the temperature of the high-speed stirring is too low, all the components cannot be melted well, so that the dispersion performance is poor, and the subsequent use effect is affected.
Finally, the invention also provides application of the modified calcium carbonate special for the polyvinyl chloride composite material in preparing polyvinyl chloride.
The modified calcium carbonate special for the polyvinyl chloride composite material has excellent stability and fluidity, can meet the performance requirements of high-performance polyvinyl chloride on calcium carbonate and additives when being used for preparing the polyvinyl chloride composite material, effectively solves the problems of poor compatibility between calcium carbonate and polyvinyl chloride, small addition amount, low material strength, poor dimensional stability, degradation in the preparation process and the like caused by poor thermal stability in the prior art on the basis of obviously increasing the addition amount of the calcium carbonate, and can effectively improve the brittleness of the polyvinyl chloride, improve the impact strength and the tensile strength of the polyvinyl chloride when being used for preparing the polyvinyl chloride composite material, and the prepared polyvinyl chloride composite material has more excellent comprehensive performance and expands the application field of the polyvinyl chloride.
Preferably, when the modified calcium carbonate is used for the polyvinyl chloride composite material, the mass ratio of the modified calcium carbonate to the polyvinyl chloride is 30-70%. The modified calcium carbonate contains the coated calcium carbonate with a specific double-layer coating structure, and is combined with the stabilizer, the processing modifier and the like with specific content, compared with the existing calcium carbonate or modified calcium carbonate, the addition amount of the calcium carbonate can be greatly increased, the performance of the polyvinyl chloride is not reduced, the comprehensive performance of the polyvinyl chloride is effectively improved, and the production cost is reduced.
The modified calcium carbonate is specially used for polyvinyl chloride composite materials, wherein the coated calcium carbonate is prepared by adopting a double-layer composite modification technology, and the double-layer coating modification is carried out on the calcium carbonate by utilizing a high-molecular polymer hyper-dispersant and a phosphate compound. The first modified layer is prepared from three different types of hyperdispersant mixtures, wherein in the mixture formed by the three different types of hyperdispersants, anchoring groups in molecular configurations and macromolecular solvation chain segments of the mixture have different molecular configurations such as single-point connection, block connection, comb connection and the like, a large number of macromolecular polar functional groups are anchored on the surfaces of calcium carbonate particles by utilizing the anchoring effect of the macromolecular polymer hyperdispersant, and then a protective layer is formed by the solvation chain, so that the calcium carbonate particles are prevented from contacting each other, the aggregation of calcium carbonate is avoided, and the hyperdispersant mixtures with multiple molecular configurations can form a firmer adsorption effect on the surfaces of the calcium carbonate on one hand, and can be tightly attached to the second modified layer on the other hand. And then adopting a phosphate compound to carry out repairable secondary modification, and carrying out surface treatment on calcium carbonate by using the phosphate compound, wherein the main reaction of phosphate and Ca 2+ on the surface of the calcium carbonate generates calcium phosphate to deposit or coat on the surface of calcium carbonate particles, so that the surface property of the calcium carbonate is changed from hydrophilicity to lipophilicity. The calcium carbonate modified by the composite modification technology has the characteristics of low price, high temperature resistance, stable chemical performance, no precipitation, strong reaction activity, capability of capturing free radicals or polar bonds of a polymer system, and the like. Meanwhile, the modified calcium carbonate is combined with a stabilizer, a processing modifier and the like with specific selection and quantity ratio, can be directly combined with polyvinyl chloride to prepare a polyvinyl chloride composite material, and compared with the existing polyvinyl chloride composite material, the modified calcium carbonate has the advantages that the compatibility of the calcium carbonate and the polyvinyl chloride is effectively improved, the mechanical property of the composite material can be improved, the filling quantity of the calcium carbonate can be improved, the comprehensive properties of the polyvinyl chloride such as impact strength and tensile strength can be improved, the processing fluidity of the polyvinyl chloride can be improved, meanwhile, the production cost is reduced, the use performance of high-end products can be met, and the application range of the polyvinyl chloride is widened.
The preparation method of the special calcium carbonate for the polyvinyl chloride composite material has simple process steps, can effectively prepare the product with stable physical properties and high product quality through the control of specific feeding sequence and process conditions, and is beneficial to industrial popularization and application. The preparation method is designed aiming at the structure and the components of the modified calcium carbonate special for the polyvinyl chloride composite material, and provides a special modified calcium carbonate product for the preparation of the polyvinyl chloride composite material.
Drawings
FIG. 1 is an exterior view of one embodiment of a coated calcium carbonate employed in the present invention;
FIG. 2 is an external view showing a comparative example of coated calcium carbonate used in the present invention;
Fig. 3 is an external view showing another comparative example of coated calcium carbonate used in the present invention.
Detailed Description
Unless otherwise specified, the raw materials used in the examples of the present invention are commercially available conventional raw materials, the equipment used is conventional equipment in the art, and the methods used are conventional methods in the art. For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, but should not be construed as limiting the invention in any way.
The calcium carbonate used in the following examples is calcium carbonate with whiteness of 96-99.5%, caCO 3 content as high as 99.5% and particle size of 1500 mesh.
Other raw materials used in the following examples are as follows:
The high molecular polymer hyperdispersants LD-1060, LD-1651, LD-300P, LD, 1300, LD-1103 are all available from resin Co., ltd;
Fatty alcohol polyoxyethylene ether phosphate, available from Nantongren chemical industry Co., ltd;
Dodecyl phosphate, purchased from the petrochemical plant, sea-safe in Jiangsu province;
Castor oil phosphate, available from south tongren chemical industry limited;
Processing modifiers ACR-201 and ACR-401 were purchased from Shanghai Hua Yi chemical auxiliary Co., ltd; b-564 was purchased from Japanese Brillouin chemical Co., ltd;
the stabilizer is dibutyl tin Dilaurate (DBTL);
The plasticizer is epoxidized soybean oil;
The lubricant is paraffin wax.
Example 1
The embodiment of the modified calcium carbonate special for the polyvinyl chloride composite material comprises the following steps:
(1) Adding calcium carbonate into a high-speed stirrer, stirring and drying until the water content is less than or equal to 0.2wt%;
(2) Diluting the high-molecular polymer hyperdispersant to 3 times of the weight of the white oil, then adding the white oil into a high-speed stirrer in the step (1) for high-speed stirring, keeping the temperature at 110 ℃ and stirring for 8 minutes to obtain calcium carbonate with the surface coated with a first modified layer;
(3) Adding the phosphate compound into the high-speed stirrer in the step (1), keeping the temperature at 110 ℃, and stirring for 8 minutes to obtain coated calcium carbonate;
(4) Slowly adding the stabilizer into the high-speed stirrer in the step (1) and keeping high-speed stirring at 110 ℃ for 6 minutes;
(5) Adding the plasticizer, the processing modifier and the lubricant into the high-speed stirrer in the step (1), stirring at a high speed for 6 minutes at 110 ℃, and then cooling to 35 ℃ to obtain the modified calcium carbonate.
In the preparation process of the modified calcium carbonate special for the polyvinyl chloride composite material in the embodiment, the material selection and the use amount of each raw material are shown in tables 1 and 2.
Examples 2 to 13 and comparative examples 1 to 6
The preparation methods of modified calcium carbonate special for polyvinyl chloride composite materials of examples 2 to 13 and comparative examples 1 to 6 are the same as those of example 1 described above, except that the coated calcium carbonate and other raw materials are used in different amounts, the raw materials for preparing the coated calcium carbonate are shown in table 1, and the raw materials for preparing the modified calcium carbonate are shown in table 2.
TABLE 1 preparation of coated calcium carbonate (weight parts)
Table 2 raw materials for preparing the modified calcium carbonate (parts by weight)
Effect example 1
The coated calcium carbonate 9, 13 and 15 were observed separately, and the coated calcium carbonate 9, 13 and 15 were grasped by hand, respectively, and it was found that the coated calcium carbonate 9 had a finer and loose feel, and the loose fine powder was recovered soon after the grasping and releasing, whereas the coated calcium carbonate 13 and 15 had some lumps of unequal sizes, and some larger lumps were formed after the grasping and releasing. The three groups of modified calcium carbonate are photographed under the same light with the same magnification, the appearance photo of the coated calcium carbonate 9 is shown in fig. 1, and the appearance photo of the coated calcium carbonate 13 and 15 is shown in fig. 2 and 3.
As can be seen from fig. 1 to 3, the coated calcium carbonate 9 is fine in powder and uniform in particles, while the coated calcium carbonates 13 and 15 have lump agglomerates of unequal numbers and sizes.
Effect example 2
Bulk Density test of coated calcium carbonate
The coated calcium carbonates 1 to 17 and the untreated initial calcium carbonate, which were prepared by the same method (corresponding steps were omitted from the raw materials lacking in the coated calcium carbonates 14 and 15) as the raw materials for preparation described in table 1, were subjected to bulk density test using GB/T23771-2009, and the test results are shown in table 3.
TABLE 3 results of bulk Density test of coated calcium carbonate for each group
As can be seen from the results in Table 3, the packing density of the coated calcium carbonates 1 to 9 was significantly reduced compared with those of coated calcium carbonates 10 to 17, which is also substantially consistent with the appearance of the product.
Compared with the coated calcium carbonate 9, the coated calcium carbonate 10 and the coated calcium carbonate 11 are mainly characterized in that the materials of the high polymer hyperdispersants are different, the inventor tests the high polymer hyperdispersants of different manufacturer types in research, and finds that products of different manufacturer types have obvious influence on the stacking density of the coated calcium carbonate, and the inventor speculates that the anchoring groups in the high polymer hyperdispersants of different types of products are different from the molecular structures formed by solvated chains, so that the activation effects of the high polymer hyperdispersants of different types of products on the coated calcium carbonate are obviously different when the high polymer hyperdispersants of different types of products are used.
The main difference between the coated calcium carbonate 12 and the coated calcium carbonate 13 and the coated calcium carbonate 9 is that the selection of the phosphate compounds is different, and the comparison shows that the selection of the phosphate compounds serving as the second modified layer is different, and has direct influence on the stacking density of the activated coated calcium carbonate, because the surfaces of the different phosphate compounds have different action groups, compared with the selection and the compounding of other phosphate compounds, the second modified layer can be better matched with the first modified layer, so that the mixture can be tightly and firmly adsorbed on the surface of calcium carbonate, and the problem of calcium carbonate agglomeration is avoided.
Compared with the coated calcium carbonate 9, the coated calcium carbonate 14 and 15 are mainly different in that the single-layer coating is adopted to coat the carbonic acid, and the comparison shows that the bulk density of the calcium carbonate coated by the single-layer coating is obviously higher than that of the double-layer coating, so that the effect of mutual coordination enhancement between the high-molecular polymer hyper-dispersant and the phosphate compound can be demonstrated when the double-layer coating is adopted, and the cooperation of the high-molecular polymer hyper-dispersant and the phosphate compound can play a better role in dispersing and activating the carbonic acid.
The main difference between the coated calcium carbonate 16 and the coated calcium carbonate 9 is that the addition amount of the modified layer is larger, and the bulk density of the coated calcium carbonate 16 does not achieve the effect smaller than that of the coated calcium carbonate 9, so that the addition amount of the modified layer material is not as large as possible, and when the addition amount of the high polymer hyperdispersant and the phosphate compound is too large, the excessive high polymer hyperdispersant and the phosphate compound are in turn used for pasting the activated and dispersed calcium carbonate to form partial agglomeration, thereby bringing adverse effects. The main difference between the coated calcium carbonate 17 and the coated calcium carbonate 2 is that the amount of the modified layer added is smaller, and the bulk density of the coated calcium carbonate 17 is significantly higher than that of the coated calcium carbonate 2 as seen from the bulk density test result, so that when the amount of the modified layer added is too small, the surface of the calcium carbonate powder cannot be completely coated, and the calcium carbonate also has partial agglomeration, and the bulk density is larger. Therefore, the addition amount of the modified layer is in a certain range, so that double-layer coating can be fully formed on the calcium carbonate powder, and the adverse effect of redundant modified layer raw materials on activated and dispersed coated calcium carbonate is avoided. The inventor of the application finds that the two modified layers are selected according to the raw materials through repeated experiments, and when the mass ratio of the modified layers to the calcium carbonate is (0.1-3): when 100, the coating activation effect is good, especially when the mass ratio of the modified layer to the calcium carbonate is (2-3): 1, has excellent coating activation effect.
Effect example 3
Performance test of polyvinyl chloride composite material prepared by adopting modified calcium carbonate
The modified calcium carbonate and the polyvinyl chloride in the examples 1-13 and the comparative examples 1-6 are respectively adopted to prepare the polyvinyl chloride composite material, the addition amount of the modified calcium carbonate is 50% of the mass of the polyvinyl chloride, each group of modified calcium carbonate and the polyvinyl chloride are added into a high-speed stirrer to be stirred and blended, then the materials are discharged and plasticated on an open mill at 170 ℃, a mold with the consistent thickness and the size of a spline is placed on a flat vulcanizing machine after the plasticated evenly, the plasticated molten materials are placed into the mold to be subjected to hot press molding, the materials are taken out after being subjected to pressure maintaining and cooling to below 40 ℃ in a cold press, and the polyvinyl chloride composite material is subjected to static relaxation at room temperature for 24 hours and then tested.
The impact strength and tensile strength of each group of polyvinyl chloride composite materials are respectively tested by the following methods:
Impact strength: adopting a GB/T1043.1-2008 plastic simply supported beam impact property measurement standard, preparing a U-shaped notch impact sample of the simply supported beam by a mechanical processing method according to the GB1043-2008 standard by a test sample, then carrying out room temperature impact test on each group of 5 samples by an impact tester, taking an average value of the 5 samples, and adopting a spline (80 mm multiplied by 10mm multiplied by 4 mm) A-shaped notch with the same specification by each group of samples;
Tensile strength: preparing a sample under the requirement of GB/T1040.2-2022 standard, and then testing the tensile strength according to GB/T1040.2-2022 standard;
the test results are shown in Table 4.
Table 4 results of impact and tensile testing of polyvinyl chloride composites of each group
As can be seen from the results of Table 4, the polyvinyl chloride composite materials prepared in examples 1 to 9 and examples 12 to 13 have good impact strength and tensile strength, and in particular, the impact strength and tensile strength properties of example 9 are particularly remarkable. In examples 10 and 11, since the types of the high molecular polymer hyperdispersant in the coated calcium carbonate are different, the first modified layer in the coated calcium carbonate is affected during the preparation process of the composite material after the prepared modified calcium carbonate is mixed with polyvinyl chloride to prepare the composite material, and the anchoring adsorption effect is reduced, so that the impact strength and the tensile strength of the prepared polyvinyl chloride composite material cannot be effectively improved.
Examples 12-13, while using the same coated calcium carbonate, have different processing modifier selections, and from the test results, it can be seen that examples 12 and 13 have significantly reduced impact strength and tensile strength compared to example 9, and that the processing modifier selections have a greater impact on the properties of the composite material in the present application, and that the polyvinyl chloride composite material produced can have excellent mechanical properties only when using the specific coated calcium carbonate in combination with the specific processing modifier selections.
Compared with the example 9, the comparison examples 1 and 2 have the advantages that the matching effect between the second modified layer and the first modified layer is reduced due to the difference of the phosphate compound selected by the second modified layer in the coated calcium carbonate, and when the modified calcium carbonate is added into polyvinyl chloride to prepare the composite material, the impact strength and the tensile strength improving effect of the modified calcium carbonate on the polyvinyl chloride are greatly reduced.
Compared with the embodiment 9, the embodiment 3 and the embodiment 4 have the advantages that the calcium carbonate is coated by the single-layer modified layer, the interaction enhancement effect between the double-layer modified layers is lost, and the impact strength and the tensile strength of the polyvinyl chloride composite material are improved greatly.
Comparative example 5 compared with example 9, the addition of more modified layers in the coated calcium carbonate brings about not only an increase in cost, but also because the addition amount of the high-molecular polymer hyperdispersant and the phosphate compound is too much, the excessive substances have no reinforcing effect on the dispersion activation of calcium carbonate, but also have adverse effects on the coated calcium carbonate which has been activated and dispersed, thereby affecting the impact strength and tensile strength of the composite material obtained.
Comparative example 6 compared with example 2, since the amount of the modified layer added in the coated calcium carbonate is too small and the calcium carbonate cannot be completely coated and activated, the impact strength and tensile strength of the obtained composite material are also remarkably reduced after the modified calcium carbonate is added to polyvinyl chloride to prepare the composite material.
In addition, the special modified calcium carbonate for the polyvinyl chloride composite material adopts the double-layer coated calcium carbonate with the specific structure and components and combines the combination of other components, and the addition amount of the calcium carbonate in the polyvinyl chloride composite material is larger, but the problems of poor processing fluidity and the like of the polyvinyl chloride are not caused, and the mechanical property of the polyvinyl chloride composite material is obviously improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. The modified calcium carbonate special for the polyvinyl chloride composite material is characterized by comprising the following components in parts by weight: 100.1-103 parts of coated calcium carbonate, 1-3 parts of stabilizer, 1-5 parts of plasticizer, 0.5-2 parts of processing modifier and 1-3 parts of lubricant;
The coated calcium carbonate comprises calcium carbonate and a modified layer coated on the surface of the calcium carbonate, and the mass ratio of the calcium carbonate to the modified layer is 100: (0.1-3);
the modified layer comprises a first modified layer coated on the surface of the calcium carbonate and a second modified layer coated on the outer surface of the first modified layer; the mass ratio of the first modified layer to the second modified layer is 1: (1-3);
the preparation raw materials of the first modified layer comprise high-molecular polymer hyperdispersant which is a mixture of LD-1060, LD-1651 and LD-300P, and the mass ratio of the components is LD-1060: (LD-1651+ld-300P) = (2-5): 1, the mass ratio of the LD-1651 to the LD-300P is (1-2): (1-2);
The preparation raw materials of the second modified layer comprise phosphate compounds, wherein the phosphate compounds are a mixture of fatty alcohol polyoxyethylene ether phosphate, dodecyl phosphate and castor oil phosphate, and the mass ratio of the components is fatty alcohol polyoxyethylene ether phosphate: dodecyl phosphate: castor oil phosphate = 4: (1-2): (1-3).
2. The modified calcium carbonate special for polyvinyl chloride composite material according to claim 1, wherein the stabilizer is at least one of tin composite stabilizer, calcium-zinc composite stabilizer, antimony composite stabilizer and rare earth composite stabilizer;
and/or the plasticizer is at least one of dihexyl sebacate, dihexyl adipate, trioctyl phosphate, tridecyl phthalate, pentaerythritol ester, trimethyl benzoate, epoxy butyl stearate, epoxy octyl stearate, epoxy soybean oil, trimethyl phosphate, tri-n-butyl citrate and phthalate;
and/or the processing modifier is at least one of acrylic ester copolymer, methyl methacrylate-butadiene-styrene copolymer and chlorinated polyethylene;
The lubricant is at least one of fatty acid lubricant, fatty acid amide lubricant and hydrocarbon lubricant.
3. The modified calcium carbonate special for polyvinyl chloride composite material according to claim 2, wherein the tin composite stabilizer is at least one selected from DBTL, DOTL, DMTFG, DBTM, DOTTG;
The calcium-zinc compound stabilizer is at least one selected from ST-901B, ST-381 and ST-905;
The antimony compound stabilizer is at least one selected from STH-1 and STH-II;
The rare earth compound stabilizer is at least one selected from stearic acid rare earth stabilizer, fatty acid rare earth stabilizer, lauric acid rare earth stabilizer, salicylic acid rare earth stabilizer, citric acid rare earth stabilizer, caprylic acid rare earth stabilizer, oleic acid rare earth stabilizer, phthalic acid monoester rare earth stabilizer, thiolate rare earth stabilizer and thiol ester based rare earth stabilizer;
The acrylic ester copolymer in the processing modifier is at least one selected from ACR-201, ACR-301, ACR-401, ACR-501, ACR-601, P-5335 and P-551; the methyl methacrylate-butadiene-styrene copolymer is selected from at least one of B-564, B-625, B-621, MR-160, MR-363, PA-20 and M-61; the chlorinated polyethylene is selected from at least one of CPE130A, CPE, 135A, CPE, 135B, CPE and 140B;
The fatty acid lubricant is stearic acid;
the fatty acid amide lubricant is at least one selected from oleamide, stearic acid amide, ethylene bis-stearamide and ethylene bis-stearamide;
The hydrocarbon lubricant is at least one selected from paraffin wax, polyethylene wax, low molecular polypropylene wax and chlorinated polyethylene wax.
4. A modified calcium carbonate special for polyvinyl chloride composite material according to claim 3, wherein the processing modifier is a mixture of ACR-201, ACR-401 and B-564, and the mass ratio thereof is: (ACR-201+acr-401): b-564= (1-5): 1.
5. A method for preparing the modified calcium carbonate special for the polyvinyl chloride composite material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) Adding calcium carbonate into a high-speed stirrer, stirring and drying until the water content is less than or equal to 0.2wt%;
(2) Diluting the high-molecular polymer hyper-dispersant with white oil, adding the white oil into a high-speed stirrer in the step (1) for high-speed stirring, keeping the temperature at 80-125 ℃ and stirring for 5-10 minutes to obtain calcium carbonate with a first modified layer coated on the surface;
(3) Adding the phosphate compound into the high-speed stirrer in the step (1), keeping the temperature at 80-125 ℃, and stirring for 5-10 minutes to obtain coated calcium carbonate;
(4) Slowly adding a stabilizer into the high-speed stirrer in the step (1) and keeping high-speed stirring at 80-125 ℃ for 5-10 minutes;
(5) And (2) adding the plasticizer, the processing modifier and the lubricant into the high-speed stirrer in the step (1), stirring at a high speed of 80-125 ℃ for 5-10 minutes, and then cooling to 35-50 ℃ to obtain the modified calcium carbonate.
6. The application of the modified calcium carbonate special for the polyvinyl chloride composite material according to any one of claims 1-4 in the polyvinyl chloride composite material.
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| CN102464839A (en) * | 2010-11-10 | 2012-05-23 | 上海华明高技术（集团）有限公司 | Composite toughening modifier for plastics and preparation method thereof |
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| KR100568412B1 (en) * | 2003-11-14 | 2006-04-05 | 주식회사 엘지화학 | PVC-PCC Nanocomposites Resin Composition with Superior Impact Strengths and Method for Preparing the Same |
| CN103896776B (en) * | 2012-12-26 | 2015-09-30 | 上海华明高技术（集团）有限公司 | Calcium carbonate surface modifying agent and preparation and application thereof |
| CN109337244A (en) * | 2018-09-28 | 2019-02-15 | 贺州钟山县双文碳酸钙新材料有限公司 | The modified calcium carbonate of coarse whiting loading can be improved |
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