CN115926093A - Composite polyether for spraying foam and preparation method thereof - Google Patents
Composite polyether for spraying foam and preparation method thereof Download PDFInfo
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- CN115926093A CN115926093A CN202211536241.9A CN202211536241A CN115926093A CN 115926093 A CN115926093 A CN 115926093A CN 202211536241 A CN202211536241 A CN 202211536241A CN 115926093 A CN115926093 A CN 115926093A
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- composite
- polyether
- polyol
- foam stabilizer
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 51
- 239000006260 foam Substances 0.000 title claims abstract description 51
- 229920000570 polyether Polymers 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000005507 spraying Methods 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 39
- 150000003077 polyols Chemical class 0.000 claims abstract description 39
- 239000003381 stabilizer Substances 0.000 claims abstract description 29
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims abstract description 28
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 19
- 229930006000 Sucrose Natural products 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000005720 sucrose Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 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 claims abstract description 10
- 239000003063 flame retardant Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 7
- -1 acrylic ester Chemical class 0.000 description 7
- 239000011496 polyurethane foam Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 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 2
- YWDFOLFVOVCBIU-UHFFFAOYSA-N 1-dimethoxyphosphorylpropane Chemical compound CCCP(=O)(OC)OC YWDFOLFVOVCBIU-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- OTOLFQXGRCJFQN-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;formate Chemical compound [O-]C=O.CC(O)C[N+](C)(C)C OTOLFQXGRCJFQN-UHFFFAOYSA-M 0.000 description 1
- WMNWJTDAUWBXFJ-UHFFFAOYSA-N 3,3,4-trimethylheptane-2,2-diamine Chemical compound CCCC(C)C(C)(C)C(C)(N)N WMNWJTDAUWBXFJ-UHFFFAOYSA-N 0.000 description 1
- DPXFJZGPVUNVOT-UHFFFAOYSA-N 3-[1,3-bis[3-(dimethylamino)propyl]triazinan-5-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCC1CN(CCCN(C)C)NN(CCCN(C)C)C1 DPXFJZGPVUNVOT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a composite polyether of spraying foam and a preparation method thereof, the composite polyether comprises a composite polyol, a catalyst, a physical foaming agent, water, a foam stabilizer and a flame retardant, wherein the physical foaming agent comprises methyl formate, the composite foam stabilizer comprises a first component which is acrylate and/or methacrylate, and the composite polyol comprises sucrose polyether polyol with a hydroxyl value of 410-440mgKOH/g and a viscosity of 4700-5700mPa.s, sucrose polyether polyol with a hydroxyl value of 430-465mgKOH/g and a viscosity of 2000-3000mPa.s and sucrose polyether polyol with a hydroxyl value of 415-445mgKOH/g and a viscosity of 4200-6200mPa.s. The polyurethane prepared by the polyether composition has the advantages of environmental protection, good flame retardance, low cost and stable storage performance.
Description
Technical Field
The invention belongs to the field of polyurethane foam, and particularly relates to composite polyether for spraying foam and a preparation method thereof.
Background
With the elimination of hydrochlorofluorocarbon foaming agents such as CFCs (carbon-hydrogen-carbon compounds), HCFCs (hydrogen-carbon compounds), water and HFO (fluoroolefins) which are foaming agents of polyurethane foam, the pentane which is commonly used in plates belongs to flammable and explosive substances and cannot be used in spray paint. And the spraying rate of the whole water is low, and the heat conductivity of the foam is high. Fourth generation blowing agents such as honeywell have low LBA boiling points and are not suitable for use in the spray application field.
Methyl formate and HFOs belong to the fourth generation physical foaming agent, the boiling point is similar to 141b, and the foaming agent has the advantages of low molecular weight, low cost, zero ODP (ozone Density plasma) and extremely low GWP, but the spraying type foam combined polyether uses the methyl formate to be extremely easy to hydrolyze in a combined polyether system to generate formic acid and methanol, and the formic acid and an amine catalyst undergo an irreversible reaction to reduce the material reaction activity and shorten the system storage time.
The applicant has designed a combination of blowing agent + foam stabilizer (methyl formate + acrylate and/or methacrylate) to solve the problem of easy hydrolysis of methyl formate in the polyether polyol, but the polyether polyol of the spray type foam still has the problem of short shelf life.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a composite polyether of spraying foam with long storage period and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a composite polyether of spraying foam comprises a composite polyol, a catalyst, a physical foaming agent, water, a foam stabilizer and a flame retardant, wherein the physical foaming agent comprises methyl formate, the composite foam stabilizer comprises a first component which is acrylate and/or methacrylate, and the composite polyol comprises 5-30 parts of sucrose polyether polyol with a hydroxyl value of 410-440mgKOH/g and a viscosity of 4700-5700mPa.s, 25-50 parts of sucrose polyether polyol with a hydroxyl value of 430-465mgKOH/g and a viscosity of 2000-3000mPa.s and 35-60 parts of sucrose polyether polyol with a hydroxyl value of 415-445mgKOH/g and a viscosity of 4200-6200mPa.s. The acrylic ester and/or the methacrylic ester play a role in emulsifying performance, improving surface tension, stabilizing foam and avoiding hydrolysis of methyl formate in the polyether system. And the same initiator sucrose polyether polyol is utilized to enable the components of the combined white material to be similar to a uniform system and have excellent storage stability, and the difference of viscosity is beneficial to the optimization of the fluidity of the combined white material.
Catalysts include blowing catalysts, gelling catalysts and trimerization catalysts. The foaming catalyst includes, but is not limited to, any one or more of pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether and tetramethylhexanediamine. The gel catalyst includes but is not limited to any one or more of N, N-dimethylcyclohexylamine, triethylene diamine, 1, 2-dimethyl imidazole and dimethylbenzylamine. The trimerization catalyst includes but is not limited to any one or more of 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2,4, 6-tris (dimethylaminomethyl) phenol, methyl quaternary ammonium salt, potassium caprylate, potassium acetate, (2-hydroxypropyl) trimethyl ammonium formate, ethyl quaternary ammonium salt and octyl quaternary ammonium salt. When two or more catalysts are used, a mixture thereof in any ratio may be used.
The flame retardant may be any known flame retardant suitable for producing polyurethane foams, and halogen-free organic phosphates such as triethyl phosphate (TEP); halogenated phosphates, such as tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP); and organic phosphonates such as dimethyl methylphosphonate (DMMP), dimethyl propylphosphonate (DMPP); or solids such as ammonium polyphosphate (APP), red phosphorus, and the like; halogenated polyols and solids such as expandable graphite, alumina, antimony compounds and melamine may also be used.
The foam stabilizer of the present invention may further comprise a silicone surfactant such as polyether siloxane and the like.
As a further improvement of the technical scheme, the composite foam stabilizer also comprises a second component which is polyether siloxane. The polyether siloxane acts synergistically with the first component, effectively improving the surface tension and dimensional stability of the composition.
As a further improvement of the technical proposal, the mass percentage of the first component in the composite foam stabilizer is 20 to 50 percent. When the first component is higher than 50%, the composite foam stabilizer has weak effect of improving the tension of the composition, is not favorable for balancing the gel tension of foam cells, and has unstable bubbles; when the content of the first component is less than 20%, the dissolution of methyl formate is not facilitated.
As a further improvement of the technical proposal, in order to achieve both foam stabilizing performance and solubility performance, the number average molecular weight of the acrylate and/or the methacrylate is 500 to 1000g/mol.
As a further improvement of the technical scheme, the combined polyether comprises, by weight, 100 parts of combined polyol, 8-10 parts of catalyst, 8-11 parts of physical foaming agent, 1-2.5 parts of water, 6-9 parts of composite foam stabilizer and 25-40 parts of flame retardant, wherein the combined polyol comprises 5-30 parts of sucrose polyether polyol with the hydroxyl value of 410-440mgKOH/g and the viscosity of 4700-5700mPa.s, 25-50 parts of sucrose polyether polyol with the hydroxyl value of 430-465mgKOH/g and the viscosity of 2000-3000mPa.s and 35-60 parts of sucrose polyether polyol with the hydroxyl value of 415-445mgKOH/g and the viscosity of 4200mPa.s. The preparation of the conjugate polyether is carried out by only ensuring that the methyl formate is mixed with the acrylate and/or methacrylate to ensure the dissolution of the methyl formate, and other operations are the same as those conventional in the art.
As a further improvement of the technical scheme, in order to ensure the dispersion and dissolution of the methyl formate, the composite polyol, the physical foaming agent, the first component of the composite foam stabilizer and the flame retardant are uniformly mixed during preparation, and then the catalyst, the water and other components of the composite foam stabilizer are added and fully mixed to obtain the composite foam stabilizer. And then adding an isocyanate, which is known in the art, such as polymethylene polyphenyl polyisocyanate (abbreviated as polymeric MDI) or modified polymeric MDI, whereinThe polymeric MDI may be selected from polymeric MDI having an average functionality of 2.7 to 2.9, such as an average functionality of 2.7,
PM200、
44v20L、/>
M20s、/>
PM2010 and the like, polymeric MDI having an average functionality of 2.9, based on the total weight of the polyol, and based on the total weight of the polyol>
M50、/>
PM400、/>
44V40L、/>
2085, and the like.
As a further improvement of the technical proposal, in order to ensure the intersolubility of the methyl formate and the first component, the mixing temperature of the physical foaming agent and the first component of the composite foam stabilizer is 20-30 ℃.
Compared with the prior art, the foam stabilizer has outstanding substantive characteristics and remarkable progress, particularly, the foam stabilizer adopts methyl formate as a physical foaming agent, is low in cost and environment-friendly, and is assisted with acrylic ester and/or methacrylic ester as a foam stabilizer to ensure the stability of the foam. Furthermore, polyether siloxane, acrylate and/or methacrylate are/is used as the composite foam stabilizer, the foam stabilizing effect is synergistically improved, and the stability and the heat insulation performance of the board are further improved. Furthermore, the combined polyether adopts the same initiator polyol combination form to ensure the uniformity and stability of the white material combination. The polyurethane foam prepared from the polyether has the advantages of environmental protection, good flame retardance and low cost, and has better storage stability.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments, but the content of the present invention is not limited to the following examples.
In the present invention, unless otherwise specified, various terms in the present invention are defined as follows:
the core density in the present invention was measured in accordance with GB/T6343-2009 "measurement of apparent density of foam and rubber". The compressive strength was determined in accordance with GB/T8813-2008 "determination of compression Properties of rigid foams". The thermal conductivity was measured according to GB/T10294-2008 "method for measuring Steady State thermal resistance and related characteristics of thermal insulation Material" for thermal protection plate. The dimensional stability is determined according to GB/T8811-2008 "method for testing the dimensional stability of rigid foams". The oxygen index was determined in accordance with GB/T2406.2-2009, part 2 of the test for determining the combustion behavior by oxygen index method for plastics, at room temperature.
Some of the raw materials used in the examples and comparative examples are as follows:
the hydroxyl value of the sucrose polyether polyol H4521 is 410-440mgKOH/g, and the viscosity is 4700-5700mPa.s;
the hydroxyl value of the sucrose polyether polyol H9211 is 430-465mgKOH/g, and the viscosity is 2000-3000mPa.s;
sucrose polyether polyol H4110 has a hydroxyl value of 415-445mgKOH/g and viscosity of 4200-6200mPa.s;
sorbitol polyether polyol H5021 has a hydroxyl value of 355-385mgKOH/g and a viscosity of 2200-4200mPa.s;
isocyanates
PM400, average functionality 2.9;
isocyanates
M20s, average functionality of 2.7.
The number average molecular weight of the acrylate used was 580 and the number average molecular weight of the methacrylate was 960.
The preparation methods of the examples and the comparative examples are as follows: uniformly mixing the combined polyol, the physical foaming agent, the first component of the composite foam stabilizer and the flame retardant in a container, wherein the mixing temperature is shown in a table 1-2; then adding the catalyst, water and other components of the composite foam stabilizer in sequence, and fully mixing to obtain the composite polyether; the composite polyether and the isocyanate are respectively injected into a charging bucket of a spraying foaming machine, sprayed in a mold frame and cured to obtain the rigid polyurethane foam, and the formula of each embodiment and comparative example and the characterization data of the prepared product are shown in tables 1-4.
Table 1 examples 1-5 material formulations and mixing temperatures
Note: in the table, "-" indicates that the corresponding component of the row was not added.
Table 2 material formulations and mixing temperatures for examples 6-8 and comparative examples note: in the table, "-" indicates that the component corresponding to the row is not added
Note: in the table, "-" indicates that the corresponding component of the row was not added.
TABLE 3 Properties and apparent masses of polyurethane foams obtained in examples 1 to 5
TABLE 4 Properties and apparent masses of polyurethane foams obtained in examples 6 to 8 and comparative example
As can be seen from tables 1-4, the acrylate and/or methacrylate can exert emulsifying properties and foam stabilizing effects in the polyether system of the present invention, avoid foam merging or foam collapse, and improve the dimensional stability of the foam. The second component of the foam stabilizer may act synergistically with the acrylate and/or methacrylate to improve foam performance.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; without departing from the spirit of the invention, it is intended to cover all modifications within the scope of the invention as claimed.
Claims (7)
1. A composite polyether of a spray type foam, which comprises a composite polyol, a catalyst, a physical foaming agent, water, a foam stabilizer and a flame retardant, and is characterized in that the physical foaming agent comprises methyl formate, the composite foam stabilizer has a first component which is acrylate and/or methacrylate, and the composite polyol consists of sucrose polyether polyol with a hydroxyl value of 410-440mgKOH/g and a viscosity of 4700-5700mPa.s, sucrose polyether polyol with a hydroxyl value of 430-465mgKOH/g and a viscosity of 2000-300mPa.s and sucrose polyether polyol with a hydroxyl value of 415-445mgKOH/g and a viscosity of 4200-6200mPa.s.
2. The composite polyether of claim 1, wherein said composite foam stabilizer further comprises a second component which is a polyether siloxane.
3. The composite polyether according to claim 1 or 2, wherein the mass percentage of the first component in the composite foam stabilizer is 20 to 50%.
4. The conjugate polyether as claimed in claim 3, wherein the number average molecular weight of the acrylate and/or methacrylate is 500 to 1000g/mol.
5. The conjugate polyether as claimed in claim 4, which consists of 100 parts by weight of conjugate polyol, 8 to 10 parts by weight of catalyst, 8 to 11 parts by weight of physical blowing agent, 1 to 2.5 parts by weight of water, 6 to 9 parts by weight of composite foam stabilizer and 25 to 40 parts by weight of flame retardant, wherein the conjugate polyol consists of 5 to 30 parts by weight of sucrose polyether polyol having a hydroxyl value of 410 to 440mgKOH/g, a viscosity of 4700 to 5700mPa.s, 25 to 50 parts by weight of sucrose polyether polyol having a hydroxyl value of 430 to 465mgKOH/g, a viscosity of 2000 to 3000mPa.s and 35 to 60 parts by weight of sucrose polyether polyol having a hydroxyl value of 415 to 445mgKOH/g and a viscosity of 4200 to 6200mPa.s.
6. A process for preparing the composite polyether according to any one of claims 1-5, wherein the composite polyol, the physical foaming agent, the first component of the composite foam stabilizer and the flame retardant are mixed uniformly, and then the catalyst, water and other components of the composite foam stabilizer are added and mixed thoroughly.
7. The production method according to claim 6, wherein the mixing temperature of the physical foaming agent and the first component of the composite foam stabilizer is 20 to 30 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115785375A (en) * | 2022-12-02 | 2023-03-14 | 红宝丽集团股份有限公司 | Hydrolysis-resistant composite polyether for foam and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075345A (en) * | 2020-08-20 | 2022-02-22 | 赢创运营有限公司 | Production of polyurethane foams |
| CN115785375A (en) * | 2022-12-02 | 2023-03-14 | 红宝丽集团股份有限公司 | Hydrolysis-resistant composite polyether for foam and preparation method thereof |
| CN115850636A (en) * | 2022-12-02 | 2023-03-28 | 红宝丽集团股份有限公司 | Storage-stable combined polyether and preparation method thereof |
| CN115947916A (en) * | 2022-12-02 | 2023-04-11 | 红宝丽集团股份有限公司 | Environment-friendly foaming combined polyether and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075345A (en) * | 2020-08-20 | 2022-02-22 | 赢创运营有限公司 | Production of polyurethane foams |
| CN115785375A (en) * | 2022-12-02 | 2023-03-14 | 红宝丽集团股份有限公司 | Hydrolysis-resistant composite polyether for foam and preparation method thereof |
| CN115850636A (en) * | 2022-12-02 | 2023-03-28 | 红宝丽集团股份有限公司 | Storage-stable combined polyether and preparation method thereof |
| CN115947916A (en) * | 2022-12-02 | 2023-04-11 | 红宝丽集团股份有限公司 | Environment-friendly foaming combined polyether and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785375A (en) * | 2022-12-02 | 2023-03-14 | 红宝丽集团股份有限公司 | Hydrolysis-resistant composite polyether for foam and preparation method thereof |
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