CN102120923B - Method for preparing high solid content polyacrylate tow cigarette filter rod adhesive in one step - Google Patents
Method for preparing high solid content polyacrylate tow cigarette filter rod adhesive in one step Download PDFInfo
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- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 44
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title abstract description 8
- 239000000853 adhesive Substances 0.000 title abstract description 7
- 229920000058 polyacrylate Polymers 0.000 title description 2
- 239000000839 emulsion Substances 0.000 claims abstract description 103
- -1 polypropylene Polymers 0.000 claims abstract description 69
- 239000004743 Polypropylene Substances 0.000 claims abstract description 47
- 229920001155 polypropylene Polymers 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010900 secondary nucleation Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 226
- 239000000203 mixture Substances 0.000 claims description 139
- 239000003795 chemical substances by application Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 238000010899 nucleation Methods 0.000 claims description 39
- 230000006911 nucleation Effects 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 15
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 230000000977 initiatory effect Effects 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004677 Nylon Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229920001778 nylon Polymers 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- AIMUHNZKNFEZSN-UHFFFAOYSA-M sodium;decane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCS([O-])(=O)=O AIMUHNZKNFEZSN-UHFFFAOYSA-M 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 18
- 239000002612 dispersion medium Substances 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 3
- 239000003292 glue Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 235000019654 spicy taste Nutrition 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 description 10
- 238000009775 high-speed stirring Methods 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229920001747 Cellulose diacetate Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- PGINMPJZCWDQNT-HUUCEWRRSA-N (-)-Eschscholtzine Natural products C1C2=CC=3OCOC=3C=C2[C@@H]2N(C)[C@H]1C1=CC(OCO3)=C3C=C1C2 PGINMPJZCWDQNT-HUUCEWRRSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- VLTOSDJJTWPWLS-UHFFFAOYSA-N pent-2-ynal Chemical compound CCC#CC=O VLTOSDJJTWPWLS-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical group CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明涉及一种聚丙烯丝束香烟过滤嘴棒粘接剂的制备方法，属于粘接剂技术领域。该粘接剂是通过原位有控制的引发二次成核，一步直接制备固体含量为60～75％、25℃时的粘度为100～300MPa·s的丙烯酸或甲基丙烯酸及其酯类聚合物乳液，以水为分散介质，不含有机溶剂。与原有方法相比，该法可一次性直接制备各种软、硬段比不同的聚合物乳液，具有制备工艺简单，能耗低，生产成本低廉等特点，所得产品具有无毒、不燃、无三废、便于储运、使用安全等特性，当用于粘接聚丙烯丝束香烟过滤嘴棒时，能有效降低香烟的辣味刺激味和焦油含量，并且具有用胶少、干燥成膜速度快可接受多种类型添加剂改性等优点。The invention relates to a preparation method of a polypropylene tow cigarette filter rod adhesive, which belongs to the technical field of adhesives. The adhesive is controlled in situ to initiate secondary nucleation, and directly prepares acrylic acid or methacrylic acid and its esters with a solid content of 60-75% and a viscosity of 100-300 MPa·s at 25°C in one step. It is a biological emulsion, with water as the dispersion medium, and does not contain organic solvents. Compared with the original method, this method can directly prepare various polymer emulsions with different soft and hard segment ratios at one time. It has the characteristics of simple preparation process, low energy consumption, and low production cost. The obtained products are non-toxic, non-flammable, No three wastes, easy storage and transportation, and safe use. When used to bond polypropylene tow cigarette filter rods, it can effectively reduce the spicy taste and tar content of cigarettes, and has the advantages of less glue and fast drying and film formation. It can accept the advantages of various types of additive modification and so on.
Description
Technical field
The present invention relates to a kind of preparation method of acrylate copolymer emulsion caking agent, be exclusively used in as polypropylene tows cigarette and add the caking agent of glue filter stick in producing, belong to the caking agent preparing technical field.
Background technology
The cigarette filter material mainly is divided into two classes, and the one, Cellulose diacetate, the 2nd, polypropylene tows, both needing through bonding processing when filter stick is produced to be used for.With the matching used caking agent of Cellulose diacetate mainly be: glycerine triacetate, 2-methyl isophthalic acid, ammediol diacetate, 2, the organic softening agent of non-volatile liquid such as 2-dimethyl PGDA and two glycerol mono acetate bulks.
For polypropylene tows, it compares the advantage such as have cheapness, raw material is easy to get with Cellulose diacetate, in being particularly suitable for, the preparation of Low-end Cigarettes filter stick, but because of the strong polarity of nothing in its molecule and hydrophilic radical, smooth surface is easily opened loose, therefore, the above-mentioned bonding organic softening agent of non-volatile liquid of Cellulose diacetate opinion that is applicable to can not use, the necessary caking agent that synthesizes specially that uses, and the caking agent master who is fit to the polypropylene tows use has:
The solution-type caking agent, the method that the resin (as: terpine resin, Gum Rosin etc.) that such caking agent mainly maybe will have an adhesiveproperties by solution polymerization directly is dissolved in organic solvent makes, and is the main caking agent that present domestic cigarette filter rod factory uses.Relevant bibliographical information mainly contains: a kind of ethanol of 70%～100% of containing is solvent, contains the caking agent (CN1044674) of Vinyl Acetate Copolymer 5%～28%; " polyolefin fiber organic solvent adhesive " (Cui Jianmin, CN1047876); " cigarette polypropylene fiber tow is gluing the research of agent " (Changde Cigarette Factory, Chinese science and technology achievement storehouse, classification number: TS426); " cigarette polypropylene fiber tow tackiness agent " (milky way chemical plant, Zhengzhou City, Chinese science and technology achievement storehouse, numbering: 94209045); " cigarette with the research of the third fine filter tip tackiness agent " (" Chinese tackiness agent " 1996,5 (1), 26-28); " the cigarette research of propene fibre filter stick tackiness agent " (" bonding " 1994,15 (3), 14-17) etc.Such caking agent is mainly take Vinyl Acetate Copolymer (PVAc), rosin ester and terpine resin, polyvinyl acetate (PVA), poly-(methyl) acrylate and multipolymer thereof etc. as main solid matter.Its solids content lower (generally speaking＜30%), dispersion medium are generally organic solvent (as: ethanol, high-flash solvent wet goods).Owing to contain a large amount of organic solvents in such caking agent, have the shortcomings such as cost height, inflammable and explosive, contaminate environment, the health that Long Term Contact can the serious harm direct labor, use at present has been under an embargo.
Water miscible liquid Compositional type caking agent, such caking agent are the modified versions of solution-type caking agent.(the horse baryon CN1224039) has been reported a kind of caking agent with the formulated polypropylene tows filter stick of cellulose acetate, inorganic polymer caking agent and plant organic polymer caking agent such as " adhesive for filter tip and manufacture method thereof "; United States Patent (USP) (US Pat 4521493) has reported that a kind of water miscible liquid caking agent is used for the caking agent of polypropylene tows filter stick, and its A component is hydrogenation ester gum, hydrogenation pentalyn or polyterpene resin; The B component is polyvinyl acetate (PVA), ethylene-vinyl acetate copolymer, vinyl acetate between to for plastic-vinylformic acid and styrene-propene acid copolymer; The mass ratio of A:B is: 5～30: 95～70; Be preferably: 5～10: 95～90.Such caking agent has disperseed a certain amount of water in organic solvent medium, avoided the inflammable and explosive shortcoming of solution-type caking agent, but still the health that can pollute environment and endanger the direct labor.
Institute of Chemistry, Academia Sinica (CN1292237) has reported a kind of " polypropylene filter for cigarette and preparation method thereof ", and the monomer of its used caking agent is tridecyl acrylate, San Hydroxyalkyl methylpropane trimethacrylate or Diethylene Glycol diacrylate.Above-mentioned caking agent monomer is surperficial with the polypropylene tows that is sprayed onto shredding after 3.0～3.5% α-Hydroxyalkyl base ketone mixes, carry out polymerization and curing makes through electron beam irradiation again.The use of this caking agent need to be reequiped existing preparation mouth rod equipment, requires precise control in the use procedure, is not easy to use, and cost is higher.
English Patent (GB1514217; GB2170391) two kinds of polypropylene tows filter stick aqueous solution type caking agents have been reported, vinyl acetate between to for plastic-EHA copolymer emulsion (solid content 47%, viscosity 100MPas) and Styrene And Butyl-acrylate copolymer emulsion (solid content 50%, viscosity 52MPas); The Amsco-Res-4125 (butadiene-styrene copolymer water in suspension emulsion) that U.S. Union Oil of Californin company produces; Rhoplex631 and Rhoplex P 376 that Rohm and Hass Company produces; The Kristalex 3100 that Hercules Incorporated company produces etc.Above-mentioned caking agent forms by a kind of copolymer emulsion, and its solid content generally is lower than 50%, needs higher resin added during use, and comprehensive cost is higher.In addition, the preparation method of above-mentioned caking agent has different significantly from the present invention.
Pollute for reducing, adapt to the requirement of safety in production and environmental protection, (synthetic method of 300～1000MPas) polymer emulsions has been carried out a large amount of research to domestic and international researchist to high solids content (greater than 65%), low viscosity, having prepared solid content is more than 70%, viscosity is the emulsion polymer of 300～500MPas multimodel particle size distribution, and its Application Areas mainly concentrates on the preparation of coating.Directly prepare mainly containing of cigarette filter stick caking agent with high solids content, low viscosity emulsion: " a kind of preparation method of polypropylene tows cigarette filter rod caking agent " (Wang Hong; Sun Yanlin etc. are CN1556164) with " a kind of polypropylene tows cigarette filter rod caking agent " (Wang Hong; Sun Yanlin etc., CN1556165).The main circulation dropping emulsion polymerisation process that adopts, blending ratio by the control mix monomer, the extraction speed of the rate of addition of mix monomer and reaction emulsion, synthetic two kinds have different soft respectively, the solids content mass percent of hard section ratio is 50～75%, viscosity in the time of 25 ℃ is acrylic or methacrylic acid and the esters polymer emulsion thereof of 200～300MPas, wherein a kind of is soft, hard section monomer mass per-cent is 20: 80～40: 60 high-hard section copolymer emulsion, another kind is soft, hard section weight percent monomer is 75: 25～55: 45 high soft section copolymer emulsion, again by two kinds of differences are soft, the polymer emulsion of hard section ratio mixes, and obtains polypropylene tows cigarette filter rod caking agent.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, invents a kind of synthetic method for preparing polypropylene tows cigarette filter rod caking agent.
The preparation method characteristic of a kind of polypropylene tows cigarette filter rod of the present invention caking agent is: the emulsion polymerisation process of the initiation secondary nucleation by control is arranged, viscosity when the solids content mass percent that the direct preparation of one step has different soft, hard section ratios is 60～75%, 25 ℃ is acrylic or methacrylic acid and the esters polymer emulsion thereof of 100～300MPas, obtains polypropylene tows cigarette filter rod caking agent.
Carry out first synthetic i.e. nucleation of large particle diameter emulsion, obtain large particle diameter polymer emulsion; And then in same system, the initiation secondary nucleation that control is arranged in position, viscosity when the solids content mass ratio that obtains latex particle size and be bivariate distribution is 60～75%, 25 ℃ is the polymer emulsion of 100～300MPas, or the like, control re-initiation three times or nucleation repeatedly also can be arranged in position, through further polymerization, obtaining emulsion particle is the high-solid content polymer emulsion of ternary or multimodel particle size distribution, and its preparation technology's concrete steps are:
1) will contain carbonatoms more than or equal to soft section monomer of acrylic or methacrylic esters of gallic acid of 4 alkane chain with contain acrylic or methacrylic acid and the ester class hard section monomer thereof of carbonatoms less than 4 alkane chain and mix by mass percentage, obtain mix monomer, soft in the mix monomer, hard section monomer mass per-cent is 20: 80～75: 25;
2) then in the reactor that agitator, reflux exchanger, inert gas protection device are housed, add the water of total water amount 15～25%, under the protection of rare gas element, be heated to 80～85 ℃; Keeping mixing speed is 80 rev/mins, after system temperature is stable, the mix monomer of a small amount of initiator of disposable adding, emulsifying agent, buffer reagent and a used mix monomer total amount 1～10% of nucleation stage, after 1～5 minute, the aqueous solution that begins simultaneously in reactor, to drip remaining mix monomer and contain buffer reagent, emulsifying agent, keep temperature and stirring velocity constant, until dropwise, the reaction times is 2～2.5 hours;
3) keep temperature of reaction be 80～85 ℃ constant, the mix monomer of a small amount of initiator of disposable adding, emulsifying agent, buffer reagent and used mix monomer total amount 5～15% of secondary nucleation stage, stirring velocity is risen to rapidly 150 rev/mins, after 3～5 minutes, keep temperature-resistant, stirring velocity is down to 80 rev/mins, the aqueous solution that begins simultaneously in reactor, to drip remaining mix monomer and contain buffer reagent, emulsifying agent, keep temperature and stirring velocity constant, until dropwise, the reaction times is 2～2.5 hours;
4) be 8 with 28% ammonia neutralization to the pH value of system, keep 80～85 ℃ temperature to continue reaction 40～80 minutes, reaction product is cooled to room temperature, with the filtration of 250 purpose nylon cloths, obtain polypropylene tows cigarette filter rod caking agent.
Soft in the mix monomer, hard section monomer mass per-cent is 20: 80～75: 25; The consumption of mix monomer is 20～60% of mix monomer total amount mass ratio in nucleation process, all the other mix monomers can be at secondaries or are repeatedly used in the nucleation process, soft, hard section monomer mass per-cent of secondary or the mix monomer that repeatedly uses in the nucleation process can be identical with a nucleation, also can be different.
In nucleation process the amount of disposable adding mix monomer be in this process mix monomer consumption mass ratio 1～10%, all the other mix monomers are by at the uniform velocity dripping, rate of addition remains the amount of mix monomer divided by the reaction times for this stage.
Secondary or repeatedly in the nucleation process amount of disposable adding mix monomer be in this process mix monomer consumption mass ratio 5～15%, all the other mix monomers are by at the uniform velocity dripping, rate of addition remains the amount of mix monomer divided by the reaction times for this stage.
Initiator is ammonium persulphate, Potassium Persulphate, benzoyl peroxide, hydrogen phosphide cumene or tertbutyl peroxide, and its consumption is identical with general emulsion polymerization.
Emulsifying agent is the Compositional type emulsifying agent, can be that in the poly-15 oxygen Vinyl Ethers of sodium lauryl sulphate, sodium laurylsulfonate, alkylphenol polyoxyethylene, nonyl, polyoxyethylene nonylphenol ether, Sodium pentadecanecarboxylate, polyoxyethylene nonylphenol ether sulfosuccinic ester disodium salt, decyl sodium sulfonate, the high-carbon fatty alcohol polyoxyethylene ether any two carry out composite, consumption is 0.1～5.0% of monomer total amount mass ratio, is preferably 1.0～2.0%.
Buffer reagent is bicarbonate of ammonia; Acrylic or methacrylic acid and ester class thereof can be vinylformic acid, methyl acrylate, Isooctyl acrylate monomer, n-butyl acrylate, methacrylic acid, methyl methacrylate or n octyl methacrylate.
Caking agent of the present invention is: this emulsion copolymers caking agent is comprised of the multipolymer of acrylic or methacrylic acid and ester class polymerisable monomer thereof, take water as dispersion medium, do not contain organic solvent, the mass percent of its solids content is 60～75%, and (mass percents of total polymerisable monomer in the system), the viscosity 25 ℃ the time are 100～300MPas.This acrylic or methacrylic acid and esters monomer thereof are to be 20: 80～75: 25 mix monomer by soft, hard section monomer mass per-cent, wherein soft section monomer refers to contain carbonatoms more than or equal to the acrylic or methacrylic esters of gallic acid monomer (as: Isooctyl acrylate monomer, n-butyl acrylate, n octyl methacrylate etc.) of 4 alkane chain, and hard section monomer refers to contain carbonatoms less than the acrylic or methacrylic acid of 4 alkane chain and the polymerisable monomer (as: vinylformic acid, methyl methacrylate, methyl acrylate etc.) of esters monomer thereof.
Synthesis technique of the present invention is: get first a part of mix monomer, after mixing according to a certain percentage, carry out letex polymerization, prepare large particle diameter emulsion, then in same reaction system, within the suitable reaction times, the in position initiation secondary nucleation of control is arranged, again further polymerization, the solids content that obtains emulsion particle and be the binary size distribution are 60～75% (mass ratioes), the viscosity 25 ℃ the time is the emulsion of 100～300MPas.The like, three nucleation of in position initiation of control also can be arranged, further polymerization obtains the high solid content emulsion that emulsion particle is the ternary size distribution again.This emulsion can be directly used in the bonding of propylene tow cigarette filter rod.The consumption of mix monomer is 20～60% (mass ratioes) of mix monomer total amount during for the first time polymerization, and all the other mix monomers can use in secondary or three nucleation processes.Soft, hard section monomer mass per-cent of the mix monomer that uses for the second time can be identical with the first time, also can be different.Specific as follows:
1, the generation (nucleation) of large particle diameter emulsion: (1) will contain carbonatoms more than or equal to soft section monomer of acrylic or methacrylic esters of gallic acid of 4 alkane chain with contain acrylic or methacrylic acid and the ester class hard section monomer thereof of carbonatoms less than 4 alkane chain and mix by mass percentage, obtain mix monomer, soft in the mix monomer, hard section monomer mass per-cent is 20: 80～75: 25; (2) in the reactor that agitator, reflux exchanger, inert gas protection device are housed, add the water of total water amount 25～50%, under the protection of rare gas element, be heated to 80～85 ℃; Keeping mixing speed is 80 rev/mins, after system temperature is stable, the mix monomer of a small amount of initiator of disposable adding, emulsifying agent, buffer reagent and used mix monomer total amount 1～10% of this stage, after 1～5 minute, the aqueous solution that begins simultaneously in reactor, to drip remaining mix monomer and contain buffer reagent, emulsifying agent, keep temperature and stirring velocity constant, until dropwise, the reaction times is 2～2.5 hours.
2, the generation of low particle size emulsion (the initiation secondary nucleation that control is arranged): after the mix monomer of a nucleation dropwises, keep temperature of reaction be 80～85 ℃ constant, the a small amount of initiator of disposable adding, emulsifying agent, (composition of this mix monomer is identical in the time of can be with a nucleation for the mix monomer of buffer reagent and used mix monomer total amount 5～15% of this stage, also can be different), stirring velocity is risen to rapidly 150 rev/mins, after 3～5 minutes, keep temperature-resistant, stirring velocity is down to 80 rev/mins, begin simultaneously in reactor, to drip remaining mix monomer and contain buffer reagent, the aqueous solution of emulsifying agent, keep temperature and stirring velocity constant, until dropwise, the reaction times is 2～2.5 hours.Then, reaction product is cooled to room temperature, filters with 250 purpose nylon cloths, can obtain the polymer emulsion binding agent.The water that uses in the reaction process is aquae destillata or deionized water, and the inert protective gas of using is nitrogen or argon gas; The resulting polymers emulsion through the food blending machine high-speed stirring after 15 minutes emulsion not stratified, its solid content is: 60～75% (mass ratioes), viscosity is: 100～300MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
The used initiator of the present invention can be ammonium persulphate, Potassium Persulphate, benzoyl peroxide, hydrogen phosphide cumene, tertbutyl peroxide, and its consumption is identical with general emulsion polymerization; Emulsifying agent can be that the poly-15 oxygen Vinyl Ethers of sodium lauryl sulphate, sodium laurylsulfonate, alkylphenol polyoxyethylene, nonyl, polyoxyethylene nonylphenol ether, Sodium pentadecanecarboxylate, polyoxyethylene nonylphenol ether sulfosuccinic ester disodium salt, decyl sodium sulfonate, high-carbon fatty alcohol polyoxyethylene ether, consumption are 0.1～5.0% (mass ratio) of monomer total amount, is preferably 1.0～2.0%; Buffer reagent is bicarbonate of ammonia; Acrylic or methacrylic acid and ester class thereof can be vinylformic acid, methyl acrylate, Isooctyl acrylate monomer, n-butyl acrylate, methacrylic acid, methyl methacrylate, n octyl methacrylate etc.
Also can contain vinylbenzene (its content be monomer total mass 3～6%) or MALEIC ANHYDRIDE (its content be monomer total mass 1～5%) in this acrylate copolymer emulsion, or contain simultaneously vinylbenzene, MALEIC ANHYDRIDE (its content be monomer total mass 3～11%), as modified monomer, to improve the physical and mechanical property of caking agent.
The high solids content polypropylene tows cigarette that the present invention adopts single stage method directly to prepare take water as dispersion medium adds glue filter stick caking agent, has good environmental protection and energy saving benefit and good use properties.Compare with above-mentioned prior art, following major advantage and positively effect arranged:
1, take water as dispersion medium, do not contain any organic solvent, effectively avoided the inevitably shortcoming such as inflammable and explosive, contaminate environment and harm direct labor health of organic solvent type and water miscible liquid Compositional type caking agent institute.
2, adopt single stage method directly to prepare various soft, hard section monomers than different copolymer emulsions, it is composite not need to carry out secondary, and production process is more succinct, and performance is more stable.
3, (organic solvent type generally is lower than 30% with the solid content of existing caking agent; Aqueous solution type 50～70%) compares solid content of the present invention higher (60～75%).Therefore, rate of drying is fast, storage and trucking costs are low, and resin added is less, and the production efficiency advantages of higher is more outstanding
4, caking agent of the present invention is easy to use, need not equipment is reequiped, and can directly use at any universal filter tip production unit.
Embodiment
Below in conjunction with embodiment the utility model is described further.Unless otherwise indicated, the composition in the example and per-cent are all by mass percentage.
Embodiment 1: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 60%, 25 ℃ is 100MPas～140MPas.Used mix monomer of nucleation of this copolymer emulsion is 60% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 20: 80; The used mix monomer of secondary nucleation is 40% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 75: 25.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.
Concrete preparation process is described below:
The generation (nucleation) of large particle diameter emulsion: in the four-hole round-bottomed flask of agitator, reflux exchanger, inert gas protection device is housed; add the 150.0g aquae destillata, passed into nitrogen 10 minutes, be heated to 85 ℃; keeping mixing speed is 80 rev/mins, adds (NH)
4S
2O
81.7g, NH
4HCO
30.3g, sodium lauryl sulphate 0.6g, nonyl gathers 15 oxygen Vinyl Ether 0.9g, mix monomer 19.8g (10 parts of butyl acrylates; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 3 parts of vinylbenzene; 55 parts of methyl methacrylates; 15 parts of methyl acrylates; 5 parts of MALEIC ANHYDRIDE).After about 3 minutes, keeping temperature of reaction is 80 ℃, drips simultaneously all the other mix monomers (376.2g) and 0.84% sodium lauryl sulphate, 0.50%NH in the four-hole bottle with the speed of 6.27g/min and 2.73g/min respectively
4HCO
3With the aqueous solution (164.0g) of the poly-15 oxygen Vinyl Ethers of 1.01% nonyl, keep reacting after about 1 hour under this condition, monomer and the aqueous solution dropwise simultaneously.Temperature of reaction is risen to 85 ℃, keep other reaction conditions constant, continue reaction 1 hour.
The generation of low particle size emulsion (the initiation secondary nucleation that control is arranged): after the footpath emulsion particle formation reaction of above-mentioned macroparticle was finished, keeping temperature of reaction was 85 ℃, and it is 150 rev/mins that mixing speed is risen to, and adds (NH)
4S
2O
81.1g, NH
4HCO
30.2g, sodium lauryl sulphate 0.4g, nonyl gathers 15 oxygen Vinyl Ether 0.5g, mix monomer 39.6g (35 parts of n-butyl acrylates; 40 parts of n octyl methacrylates; 1 part in vinylformic acid; 2 parts of vinylbenzene; 21 parts of methyl methacrylates; 1 part of MALEIC ANHYDRIDE).After about 5 minutes, keeping temperature of reaction is 80 ℃, and stirring velocity is down to 80 rev/mins, drips simultaneously all the other mix monomers (224.4g) and 0.84% sodium lauryl sulphate, 0.50%NH in the four-hole bottle with the speed of 3.74g/min and 3.05g/min respectively
4HCO
3With the aqueous solution (183.0g) of the poly-15 oxygen Vinyl Ethers of 1.01% nonyl, keep reacting after about 1 hour under this condition, monomer and the aqueous solution dropwise simultaneously, and the ammonia neutralization with 28% to the pH value of system is 8.Temperature of reaction is risen to 85 ℃, keep other reaction conditions constant, continue reaction 1 hour.Then reaction product is cooled to room temperature, gets final product with the filtration of 250 purpose nylon cloths.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 60%; Viscosity is: 130MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
Embodiment 2: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 75%, 25 ℃ is 200MPas～300MPas.Used mix monomer of nucleation of this copolymer emulsion is 40% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 50: 50; The used mix monomer of secondary nucleation is 60% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 50: 50.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.
Concrete preparation process is described below:
The generation (nucleation) of large particle diameter emulsion: in the four-hole round-bottomed flask of agitator, reflux exchanger, inert gas protection device is housed; add the 150.0g aquae destillata, passed into nitrogen 10 minutes, be heated to 85 ℃; keeping mixing speed is 80 rev/mins, adds (NH)
4S
2O
82.1g, NH
4HCO
30.6g, sodium lauryl sulphate 0.9g, nonyl gathers 15 oxygen Vinyl Ether 1.2g, mix monomer 52.8g (40 parts of butyl acrylates; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 3 parts of vinylbenzene; 25 parts of methyl methacrylates; 20 parts of methyl acrylates).After about 3 minutes, keeping temperature of reaction is 80 ℃, drips simultaneously all the other mix monomers (475.2g) and 1.10% sodium lauryl sulphate, 0.60%NH in the four-hole bottle with the speed of 5.28g/min and 1.33g/min respectively
4HCO
3With the aqueous solution (120.0g) of the poly-15 oxygen Vinyl Ethers of 1.80% nonyl, keep reacting after about 1.5 hours under this condition, monomer and the aqueous solution dropwise simultaneously.Temperature of reaction is risen to 85 ℃, keep other reaction conditions constant, continue reaction 1 hour.
The generation of low particle size emulsion (the initiation secondary nucleation that control is arranged): after the footpath emulsion particle formation reaction of above-mentioned macroparticle was finished, keeping temperature of reaction was 85 ℃, and it is 150 rev/mins that mixing speed is risen to, and adds (NH)
4S
2O
83.2g, NH
4HCO
30.8g, sodium lauryl sulphate 1.2g, nonyl gathers 15 oxygen Vinyl Ether 1.8g, mix monomer 79.2g (40 parts of butyl acrylates; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 3 parts of vinylbenzene; 25 parts of methyl methacrylates; 20 parts of methyl acrylates).After about 5 minutes, keeping temperature of reaction is 80 ℃, and stirring velocity is down to 80 rev/mins, drips simultaneously all the other mix monomers (712.8g) and 1.10% sodium lauryl sulphate, 0.60%NH in the four-hole bottle with the speed of 7.92g/min and 2.00g/min respectively
4HCO
3With the aqueous solution (180.0g) of the poly-15 oxygen Vinyl Ethers of 1.80% nonyl, keep reacting after about 1.5 hours under this condition, monomer and the aqueous solution dropwise simultaneously, and the ammonia neutralization with 28% to the pH value of system is 8.Temperature of reaction is risen to 85 ℃, keep other reaction conditions constant, continue reaction 1 hour.Then reaction product is cooled to room temperature, gets final product with the filtration of 250 purpose nylon cloths.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 75%; Viscosity is: 290MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
Embodiment 3: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 68%, 25 ℃ is 200MPas～300MPas.Used mix monomer of nucleation of this copolymer emulsion is 20% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 75: 25; The used mix monomer of secondary nucleation is 80% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 40: 60.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.
Concrete preparation process is described below:
The generation (nucleation) of large particle diameter emulsion: in the four-hole round-bottomed flask of agitator, reflux exchanger, inert gas protection device is housed; add the 150.0g aquae destillata, passed into nitrogen 10 minutes, be heated to 85 ℃; keeping mixing speed is 80 rev/mins, adds (NH)
4S
2O
80.8g, NH
4HCO
30.2g, sodium lauryl sulphate 0.2g, nonyl gathers 15 oxygen Vinyl Ether 0.3g, mix monomer 3.7g (60 parts of butyl acrylates; 15 parts of n octyl methacrylates; 2 parts in vinylformic acid; 3 parts of vinylbenzene; 15 parts of methyl methacrylates; 5 parts of methyl acrylates).After about 3 minutes, keeping temperature of reaction is 80 ℃, drips simultaneously all the other mix monomers (183.3g) and 0.95% sodium lauryl sulphate, 0.50%NH in the four-hole bottle with the speed of 3.06g/min and 1.00g/min respectively
4HCO
3With the aqueous solution (60.0g) of the poly-15 oxygen Vinyl Ethers of 1.3% nonyl, keep reacting after about 1 hour under this condition, monomer and the aqueous solution dropwise simultaneously.Temperature of reaction is risen to 85 ℃, keep other reaction conditions constant, continue reaction 1 hour.
The generation of low particle size emulsion (the initiation secondary nucleation that control is arranged): after the footpath emulsion particle formation reaction of above-mentioned macroparticle was finished, keeping temperature of reaction was 85 ℃, and it is 150 rev/mins that mixing speed is risen to, and adds (NH)
4S
2O
82.8g, NH
4HCO
30.6g, sodium lauryl sulphate 0.8g, nonyl gathers 15 oxygen Vinyl Ether 1.0g, mix monomer 37.4g (30 parts of n-butyl acrylates; 10 parts of n octyl methacrylates; 1 part in vinylformic acid; 2 parts of vinylbenzene; 45 parts of methyl methacrylates; 10 parts of methyl acrylates; 2 parts of MALEIC ANHYDRIDE).After about 5 minutes, keeping temperature of reaction is 80 ℃, and stirring velocity is down to 80 rev/mins, drips simultaneously all the other mix monomers (710.6g) and 0.95% sodium lauryl sulphate, 0.50%NH in the four-hole bottle with the speed of 7.89g/min and 2.67g/min respectively
4HCO
3With the aqueous solution (240.0g) of the poly-15 oxygen Vinyl Ethers of 1.3% nonyl, keep reacting after about 1.5 hours under this condition, monomer and the aqueous solution dropwise simultaneously, and the ammonia neutralization with 28% to the pH value of system is 8.Temperature of reaction is risen to 85 ℃, keep other reaction conditions constant, continue reaction 1 hour.Then reaction product is cooled to room temperature, gets final product with the filtration of 250 purpose nylon cloths.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 68%; Viscosity is: 280MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
Embodiment 4: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 70%, 25 ℃ is 200MPas～300MPas.Used mix monomer of nucleation of this copolymer emulsion is 30% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 65: 35; The used mix monomer of secondary nucleation is 70% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 40: 60.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.Concrete preparation process:
The generation (nucleation) of large particle diameter emulsion: the consisting of of mix monomer: 40 parts of butyl acrylates; 15 parts of Isooctyl acrylate monomers; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 2 parts of vinylbenzene; 25 parts of methyl methacrylates; 6 parts of methyl acrylates.The amount that adds first mix monomer is 15.4g, and the rate of addition of mix monomer is 4.88g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 3.
The generation of low particle size emulsion (the initiation secondary nucleation that control is arranged): the consisting of of mix monomer: 25 parts of butyl acrylates; 5 parts of Isooctyl acrylate monomers; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 3 parts of vinylbenzene; 30 parts of methyl methacrylates; 20 parts of methyl acrylates; 5 parts of MALEIC ANHYDRIDE.The amount that adds first mix monomer is 71.8g, and the rate of addition of mix monomer is 7.18g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 3.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 70%; Viscosity is: 280MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
Embodiment 5: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 65%, 25 ℃ is 100MPas～230MPas.Used mix monomer of nucleation of this copolymer emulsion is 50% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 40: 60; The used mix monomer of secondary nucleation is 50% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 60: 40.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.Concrete preparation process: large grain is through the generation (nucleation) of emulsion: the consisting of of mix monomer: 30 parts of butyl acrylates; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 48 parts of methyl methacrylates; 10 parts of methyl acrylates.The amount that adds first mix monomer is 20.5g, and the rate of addition of mix monomer is 6.48g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 1.Granule is through the generation (the initiation secondary nucleation that control is arranged) of emulsion: the consisting of of mix monomer: 35 parts of butyl acrylates; 10 parts of Isooctyl acrylate monomers; 15 parts of n octyl methacrylates; 2 parts in vinylformic acid; 2 parts of vinylbenzene; 15 parts of methyl methacrylates; 20 parts of methyl acrylates; 1 part of MALEIC ANHYDRIDE.The amount that adds first mix monomer is 40.9g, and the rate of addition of mix monomer is 6.14g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 1.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 65%; Viscosity is: 180MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
Embodiment 6: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 60%, 25 ℃ is 100MPas～200MPas.Used mix monomer of nucleation of this copolymer emulsion is 30% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 55: 45; The used mix monomer of secondary nucleation is 70% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 45: 55.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.Concrete preparation process: large grain is through the generation (nucleation) of emulsion: the consisting of of mix monomer: 40 parts of butyl acrylates; 5 parts of Isooctyl acrylate monomers; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 2 parts of vinylbenzene; 25 parts of methyl methacrylates; 16 parts of methyl acrylates.The amount that adds first mix monomer is 9.9g, and the rate of addition of mix monomer is 3.14g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 1.Granule is through the generation (the initiation secondary nucleation that control is arranged) of emulsion: the consisting of of mix monomer: 25 parts of butyl acrylates; 10 parts of Isooctyl acrylate monomers; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 2 parts of vinylbenzene; 30 parts of methyl methacrylates; 20 parts of methyl acrylates; 1 part of MALEIC ANHYDRIDE.The amount that adds first mix monomer is 46.2g, and the rate of addition of mix monomer is 6.93g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 1.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 60%; Viscosity is: 160MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
Embodiment 7: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 72%, 25 ℃ is 200MPas～300MPas.Used mix monomer of nucleation of this copolymer emulsion is 50% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 20: 80; The used mix monomer of secondary nucleation is 50% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 65: 35.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.Concrete preparation process: large grain is through the generation (nucleation) of emulsion: the consisting of of mix monomer: 10 parts of butyl acrylates; 5 parts of Isooctyl acrylate monomers; 5 parts of n octyl methacrylates; 2 parts in vinylformic acid; 50 parts of methyl methacrylates; 28 parts of methyl acrylates.The amount that adds first mix monomer is 28.3g, and the rate of addition of mix monomer is 5.96g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 2.Granule is through the generation (the initiation secondary nucleation that control is arranged) of emulsion: the consisting of of mix monomer: 45 parts of butyl acrylates; 10 parts of Isooctyl acrylate monomers; 10 parts of n octyl methacrylates; 2 parts in vinylformic acid; 2 parts of vinylbenzene; 25 parts of methyl methacrylates; 5 parts of methyl acrylates; 1 part of MALEIC ANHYDRIDE.The amount that adds first mix monomer is 56.5g, and the rate of addition of mix monomer is 5.65g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 2.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 71%; Viscosity is: 280MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
Embodiment 8: should mainly be comprised of the multipolymer of acrylicacidandesters or methacrylic ester polymerisable monomer as the emulsion copolymers of polypropylene tows cigarette filter rod caking agent, take water as dispersion medium, do not contain organic solvent, the viscosity the when mass percent of its solids content is 75%, 25 ℃ is 200MPas～300MPas.Used mix monomer of nucleation of this copolymer emulsion is 60% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 55: 45; The used mix monomer of secondary nucleation is 40% of monomer total amount, and the monomer whose ratio of mixture is soft, hard section monomer mass per-cent 20: 80.Adopt " single stage method " directly to carry out emulsion polymerization, prepared polymer emulsion can be directly used in the bonding of polypropylene tows filter stick.Concrete preparation process: large grain is through the generation (nucleation) of emulsion: the consisting of of mix monomer: 40 parts of butyl acrylates; 10 parts of Isooctyl acrylate monomers; 5 parts of n octyl methacrylates; 2 parts in vinylformic acid; 38 parts of methyl methacrylates; 5 parts of methyl acrylates.The amount that adds first mix monomer is 39.6g, and the rate of addition of mix monomer is 8.36g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 2.Granule is through the generation (the initiation secondary nucleation that control is arranged) of emulsion: the consisting of of mix monomer: 10 parts of butyl acrylates; 5 parts of Isooctyl acrylate monomers; 5 parts of n octyl methacrylates; 2 parts in vinylformic acid; 58 parts of methyl methacrylates; 20 parts of methyl acrylates.The amount that adds first mix monomer is 52.8g, and the rate of addition of mix monomer is 5.28g/min, and reaction unit, operation steps and all the other proportioning raw materials are with embodiment 2.After 15 minutes, emulsion is not stratified through the food blending machine high-speed stirring for the resulting polymers emulsion; Its solid content is about: 75%; Viscosity is: 290MPas (NDJ-1 type rotational viscosimeter; 25 ℃).
The main performance index that connects agent with the polymer emulsion of the inventive method preparation is:
1), total solid content (%): 60～75
2), viscosity (MPas, 25 ℃): 100～300
3), outward appearance: white emulsion
4), unreacted monomer (%) :≤0.2
5), mouth rod hardness * (%): 90～95
6), drying at room temperature set time (hour) :≤20
7), resin added is (with dried cigarette holder restatement, %) :≤10
Annotate: the expression formula of this hardness of * is: [mouth rod green diameter (mm)-mouth rod is subject to the deformation (mm/100) that 2.94N/15s hits rear diameter]/mouth rod green diameter
Claims (8)
1. the preparation method of a polypropylene tows cigarette filter rod caking agent is characterized in that carrying out first the synthetic of large particle diameter emulsion is a nucleation, obtains large particle diameter polymer emulsion; And then in same system, the initiation secondary nucleation that control is arranged in position, the emulsion polymerisation process of the initiation secondary nucleation by control is arranged, it is that having of bivariate distribution is different soft that one step directly prepared latex particle size, the solids content mass percent of hard section ratio is 60～75%, viscosity in the time of 25 ℃ is acrylic or methacrylic acid and the esters polymer emulsion thereof of 100～300mPas, obtain polypropylene tows cigarette filter rod caking agent, the like, repeatedly nucleation of control re-initiation also can be arranged in position, through further polymerization, obtaining emulsion particle is the high-solid content polymer emulsion of multimodel particle size distribution;
Preparation technology's concrete steps are:
1) will contain carbonatoms more than or equal to soft section monomer of acrylic or methacrylic esters of gallic acid of 4 alkane chain with contain acrylic or methacrylic acid and the ester class hard section monomer thereof of carbonatoms less than 4 alkane chain and mix by mass percentage, obtain mix monomer, soft in the mix monomer, hard section monomer mass per-cent is 20: 80～75: 25;
2) then in the reactor that agitator, reflux exchanger, inert gas protection device are housed, add the water of total water amount 15～25%, under the protection of rare gas element, be heated to 80～85 ℃; Keeping mixing speed is 80 rev/mins, after system temperature is stable, the mix monomer of a small amount of initiator of disposable adding, emulsifying agent, buffer reagent and a used mix monomer total amount 1～10% of nucleation stage, after 1～5 minute, the aqueous solution that begins simultaneously in reactor, to drip remaining mix monomer and contain buffer reagent, emulsifying agent, keep temperature and stirring velocity constant, until dropwise, the reaction times is 2～2.5 hours;
3) keep temperature of reaction be 80～85 ℃ constant, the mix monomer of a small amount of initiator of disposable adding, emulsifying agent, buffer reagent and used mix monomer total amount 5～15% of secondary nucleation stage, stirring velocity is risen to rapidly 150 rev/mins, after 3～5 minutes, keep temperature-resistant, stirring velocity is down to 80 rev/mins, the aqueous solution that begins simultaneously in reactor, to drip remaining mix monomer and contain buffer reagent, emulsifying agent, keep temperature and stirring velocity constant, until dropwise, the reaction times is 2～2.5 hours;
4) be 8 with 28% ammonia neutralization to the pH value of system, keep 80～85 ℃ temperature to continue reaction 40～80 minutes, reaction product is cooled to room temperature, with the filtration of 250 purpose nylon cloths, obtain polypropylene tows cigarette filter rod caking agent.
2. the preparation method of a kind of polypropylene tows cigarette filter rod caking agent according to claim 1 is characterized in that soft in the mix monomer, hard section monomer mass per-cent is 20: 80～75: 25; The consumption of mix monomer is 20～60% of mix monomer total amount quality in nucleation process, all the other mix monomers can be at secondaries or are repeatedly used in the nucleation process, soft, hard section monomer mass per-cent of secondary or the mix monomer that repeatedly uses in the nucleation process can be identical with a nucleation, also can be different.
3. the preparation method of a kind of polypropylene tows cigarette filter rod caking agent according to claim 1, the amount that it is characterized in that disposable adding mix monomer in nucleation process is 1～10% of mix monomer consumption quality in this process, all the other mix monomers are by at the uniform velocity dripping, and rate of addition remains the amount of mix monomer divided by the reaction times for this stage.
4. the preparation method of a kind of polypropylene tows cigarette filter rod caking agent according to claim 1, it is characterized in that secondary or repeatedly in the nucleation process amount of disposable adding mix monomer be 5～15% of mix monomer consumption quality in this process, all the other mix monomers are by at the uniform velocity dripping, and rate of addition remains the amount of mix monomer divided by the reaction times for this stage.
5. the preparation method of a kind of polypropylene tows cigarette filter rod caking agent according to claim 1 is characterized in that initiator is ammonium persulphate, Potassium Persulphate, benzoyl peroxide, hydrogen phosphide cumene or tertbutyl peroxide.
6. the preparation method of a kind of polypropylene tows cigarette filter rod caking agent according to claim 1, it is characterized in that emulsifying agent is the Compositional type emulsifying agent, it is composite that the Compositional type emulsifying agent is that in the poly-15 oxygen Vinyl Ethers of sodium lauryl sulphate, sodium laurylsulfonate, alkylphenol polyoxyethylene, nonyl, polyoxyethylene nonylphenol ether, Sodium pentadecanecarboxylate, polyoxyethylene nonylphenol ether sulfosuccinic ester disodium salt, decyl sodium sulfonate, the high-carbon fatty alcohol polyoxyethylene ether any two carry out, and consumption is 0.1～5.0% of monomer total amount quality.
7. the preparation method of a kind of polypropylene tows cigarette filter rod caking agent according to claim 6 is characterized in that described consumption is 1.0～2.0% of monomer total amount quality.
8. the preparation method of a kind of polypropylene tows cigarette filter rod caking agent according to claim 1 is characterized in that buffer reagent is bicarbonate of ammonia; Acrylic or methacrylic acid and ester class thereof are selected from vinylformic acid, methyl acrylate, Isooctyl acrylate monomer, n-butyl acrylate, methacrylic acid, methyl methacrylate or n octyl methacrylate.
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| CN111607339B (en) * | 2020-06-02 | 2022-01-04 | 长沙乐远化工科技有限公司 | Nozzle glue for impermeable tipping paper and preparation method thereof |
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| CN1556164A (en) * | 2003-12-31 | 2004-12-22 | 昆明理工大学 | A kind of preparation method of polypropylene tow cigarette filter stick adhesive |
| US20080245376A1 (en) * | 2005-08-27 | 2008-10-09 | John Travers | Process For Making Filter Tow |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556164A (en) * | 2003-12-31 | 2004-12-22 | 昆明理工大学 | A kind of preparation method of polypropylene tow cigarette filter stick adhesive |
| US20080245376A1 (en) * | 2005-08-27 | 2008-10-09 | John Travers | Process For Making Filter Tow |
Non-Patent Citations (1)
| Title |
|---|
| 刘建平等.高固含量丙烯酸酯乳液的合成条件与乳液性质研究.《昆明理工大学学报（理工版）》.2007,第32卷(第5期),第5-8页，第1.1,1.2,2.1,2.2节，表1. * |
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