CN108690185B - Modified phthalic anhydride polyester polyol, composite polyether, polyurethane foam raw material composition, polyurethane foam and preparation method thereof - Google Patents
Modified phthalic anhydride polyester polyol, composite polyether, polyurethane foam raw material composition, polyurethane foam and preparation method thereof Download PDFInfo
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- CN108690185B CN108690185B CN201710229744.4A CN201710229744A CN108690185B CN 108690185 B CN108690185 B CN 108690185B CN 201710229744 A CN201710229744 A CN 201710229744A CN 108690185 B CN108690185 B CN 108690185B
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- phthalic anhydride
- polyester polyol
- polyurethane foam
- temperature
- esterification reaction
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- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 51
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 44
- 229920000570 polyether Polymers 0.000 title claims abstract description 44
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 41
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000002994 raw material Substances 0.000 title claims abstract description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000005886 esterification reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940031723 1,2-octanediol Drugs 0.000 claims abstract description 4
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 24
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 20
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- 239000006260 foam Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229920001228 polyisocyanate Polymers 0.000 claims description 14
- 239000005056 polyisocyanate Substances 0.000 claims description 14
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- 235000011056 potassium acetate Nutrition 0.000 claims description 8
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- IXNCIJOVUPPCOF-UHFFFAOYSA-N 2-ethylhexan-1-ol;titanium Chemical compound [Ti].CCCCC(CC)CO.CCCCC(CC)CO.CCCCC(CC)CO.CCCCC(CC)CO IXNCIJOVUPPCOF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims 5
- 230000000630 rising effect Effects 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 10
- 125000003118 aryl group Chemical group 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical group CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 5
- -1 dimethyl siloxane Chemical class 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/14—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides modified phthalic anhydride polyester polyol, composite polyether, a polyurethane foam raw material composition, polyurethane foam and a preparation method thereof. The preparation method of the modified phthalic anhydride polyester polyol comprises the following steps: under the catalyst and protective atmosphere, carrying out normal pressure esterification reaction and negative pressure esterification reaction in sequence on diethylene glycol, phthalic anhydride and alkane alcohol; wherein the mass ratio of the diethylene glycol to the phthalic anhydride to the alkane alcohol is (4-6): (2-3): (0.02-0.03); the alkane alcohol is one or more of neopentyl glycol, isoprene glycol and 1, 2-octanediol; the temperature and the time of the normal pressure esterification reaction are respectively 180-250 ℃ and 7-8 h; the temperature and the time of the negative pressure esterification reaction are respectively 170-210 ℃ and 2-4 h. The obtained modified aromatic polyester polyol has good compatibility with pentane, and the obtained polyurethane foam has fine and smooth pores, good hardness, stable structure, low shrinkage, good heat preservation effect and excellent flame retardance.
Description
Technical Field
The invention relates to modified phthalic anhydride polyester polyol, composite polyether, a polyurethane foam raw material composition, polyurethane foam and a preparation method thereof.
Background
Rigid polyurethane foam (polyurethane foam for short) is widely used as various heat insulating, shock-proof, sound insulating materials, lightweight structural members, packaging materials, etc. because of its superior performance, simple molding and convenient construction. As is well known, polyols for preparing polyurethane foams are mainly classified into polyether polyols and polyester polyols, and polyester polyols are classified into aliphatic polyester polyols and aromatic polyester polyols. However, since benzene rings are introduced into the molecular structure of aromatic polyester polyols, polyurethane foams obtained therefrom have advantages of high strength, good toughness, excellent flame retardancy, and the like, and thus are receiving increasing attention. At present, domestic aromatic polyester polyol is mostly prepared by adopting phthalic anhydride and diethylene glycol as raw materials, the compatibility of the aromatic polyester polyol with a physical foaming agent is poor, and the aromatic polyester polyol is limited in application because the physical foaming agent is mainly pentane at present.
Disclosure of Invention
The invention aims to overcome the defect of poor compatibility of aromatic polyester polyol and a physical foaming agent pentane in the prior art, and provides modified phthalic anhydride polyester polyol with good compatibility with pentane, composite polyether, a polyurethane foam raw material composition, polyurethane foam and a preparation method thereof. The modified aromatic polyester polyol has good compatibility with pentane, and the obtained polyurethane foam has fine and smooth pores, good hardness, stable structure, low shrinkage, good heat preservation effect and excellent flame retardance.
The invention provides a preparation method of modified phthalic anhydride polyester polyol, which comprises the following steps:
(1) carrying out normal pressure esterification reaction on diethylene glycol, phthalic anhydride and alkane alcohol under the conditions of a catalyst and a protective atmosphere to obtain a mixture A;
(2) carrying out negative pressure esterification reaction on the obtained mixture A;
wherein the mass ratio of the diethylene glycol to the phthalic anhydride to the alkane alcohol is (4-6): (2-3): (0.02-0.03); the alkane alcohol is one or more of neopentyl glycol, isoprene glycol and 1, 2-octanediol; the temperature of the normal pressure esterification reaction is 180-250 ℃, and the time of the normal pressure esterification reaction is 7-8 h; the temperature of the negative pressure esterification reaction is 170-210 ℃, and the time of the negative pressure esterification reaction is 2-4 h.
In the present invention, before the normal pressure esterification reaction, the diethylene glycol is preferably heated to 100 to 120 ℃, for example, 110 ℃, and then mixed with the phthalic anhydride and the alkane alcohol.
In the invention, the amount of the catalyst can be conventional in the field, and the mass ratio of the diethylene glycol to the catalyst is preferably (4-6): (0.0001 to 0.003).
In the present invention, the catalyst is an esterification catalyst conventionally used in the art, preferably one or more of n-butyl titanate, isopropyl titanate, titanium tetrakis (2-ethyl hexanol) and tetraisooctyl titanate, more preferably n-butyl titanate and/or isopropyl titanate.
In the present invention, the protective atmosphere is a protective atmosphere conventionally used in the art, and preferably a nitrogen atmosphere.
In the present invention, the normal pressure esterification reaction preferably includes a temperature raising process and a temperature maintaining process. The temperature of the temperature raising process is preferably 180 to 250 ℃, more preferably 180 to 230 ℃, the time of the temperature raising process is preferably 5 to 7 hours, and the temperature raising rate of the temperature raising process is preferably 8 to 12 ℃/h, for example, 10 ℃/h. The temperature in the heat preservation process is preferably 230-250 ℃, and the time in the heat preservation process is preferably 1-2 hours.
In the present invention, water is distilled off during the normal pressure esterification reaction, and in order to smoothly perform the normal pressure esterification reaction, the temperature above the esterification reaction is preferably controlled not to exceed 100 ℃, for example, may be 90 ℃.
In the present invention, the acid value of the mixture A is preferably not more than 10mgKOH/g, and may be, for example, 8mgKOH/g, 8.5mgKOH/g, 9mgKOH/g, 9.5mgKOH/g or 9.6 mgKOH/g. The acid value is preferably measured at a temperature above the esterification reaction which is reduced to 55 to 60 ℃.
In the present invention, the temperature of the negative pressure esterification reaction is preferably 180 to 200 ℃. The time of the negative pressure esterification reaction is preferably 2.1-4 hours. The vacuum degree of the negative pressure esterification reaction is preferably 0.05 to 0.09MPa, for example, 0.08 MPa.
In the invention, after the negative pressure esterification reaction, the temperature is preferably reduced to 60-100 ℃, and then the materials are discharged; and further, after the temperature is reduced to 60-80 ℃, discharging the material.
The invention also provides the modified phthalic anhydride polyester polyol prepared by the preparation method, wherein the acid value of the modified phthalic anhydride polyester polyol is less than or equal to 1.0mgKOH/g, the viscosity at 25 ℃ is 2000-4500 mPa & s, and the hydroxyl value is 50-500 mgKOH/g.
In the present invention, the acid value of the modified phthalic anhydride polyester polyol is preferably not more than 0.92mgKOH/g, and may be, for example, 0.9mgKOH/g, 0.83mgKOH/g, 0.8mgKOH/g or 0.72 mgKOH/g.
In the invention, the viscosity of the modified phthalic anhydride polyester polyol at 25 ℃ is preferably 2470-2730 mPa & s.
In the present invention, the hydroxyl value of the modified phthalic anhydride polyester polyol is preferably 200 to 250mgKOH/g, and may be, for example, 225mgKOH/g, 230mgKOH/g, 232mgKOH/g, 235mgKOH/g or 237 mgKOH/g.
The invention also provides the combined polyether, which comprises the following components in parts by mass: 40-45 parts of modified phthalic anhydride polyester polyol, 55-60 parts of polyether polyol, 2-3 parts of foam stabilizer, 0.7-1.2 parts of amine catalyst, 1.1-1.6 parts of metal catalyst, 2.5-3 parts of water and 12-14 parts of cyclopentane; the metal catalyst comprises 0.7-1 part of potassium isooctanoate and 0.4-0.6 part of potassium acetate.
In the present invention, a modifier, such as soybean oil, which is conventionally used in the art, may also be included in the composite polyether. The composite polyether may further include a flame retardant conventionally used in the art.
The invention also provides a preparation method of the combined polyether, and the preparation method of the polyether is that the components are stirred and mixed according to the conventional method in the field.
The invention also provides a polyurethane foam raw material composition, which comprises the following components: the conjugate polyether and polymethine polyphenyl polyisocyanate.
In the invention, the mass ratio of the combined polyether to the polymethine polyphenyl polyisocyanate is preferably (0.9-1): (1.2-1.5).
Before the polyurethane foam raw material composition is used, the combined polyether and the polymethine polyphenyl polyisocyanate are not contacted with each other all the time, so the polyurethane foam raw material composition can be sold and stored in a sleeved mode, and the combined polyether and the polymethine polyphenyl polyisocyanate are mixed when the polyurethane foam raw material composition is used.
The invention also provides a preparation method of the polyurethane foam, which comprises the following steps: and mixing the combined polyether and the polymethine polyphenyl polyisocyanate.
In the present invention, the mixing is preferably performed by stirring, the rotation speed of the stirring is preferably 8000 to 10000r/min, and the stirring time is preferably 8 to 12s, for example, 10 s.
The invention also provides polyurethane foam prepared by the preparation method.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the modified phthalic anhydride polyester polyol prepared by the formula has high purity, low viscosity, high activity and good compatibility with cyclopentane. The modified phthalic anhydride polyester polyol is applied to polyurethane foam, and the obtained polyurethane foam has the advantages of high strength of foam holes, high hardness, good flame retardant property, fine and smooth foam holes, good mechanical property and good heat preservation effect.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The starting materials used in the following examples are all commercially available.
In the following examples, the viscosity of the modified phthalic anhydride polyester polyol was measured at 25 ℃ using a rotational viscometer, and the specific parameters were as follows: no. 3 rotor, the rotating speed is 120 r/min.
The mass ratios of the raw materials in the following examples are shown in the following table:
example 1
(1) Preparation of modified phthalic anhydride polyester polyol
Installing a reflux condenser pipe on a four-neck flask, adding diethylene glycol, heating to 110 ℃ under stirring, then adding phthalic anhydride, neopentyl glycol and a catalyst of tetraisopropyl titanate, introducing nitrogen, distilling off water when the temperature is increased to 180 ℃, starting normal-pressure esterification reaction, heating at a heating rate of 10 ℃/h, heating to 230 ℃, controlling the temperature above the normal-pressure esterification reaction to be 90 ℃ in the heating process, maintaining for 2 hours at 230 ℃, reducing the temperature to 55 ℃, sampling and measuring the acid value, wherein the acid value is 8mgKOH/g, and completing the normal-pressure esterification reaction; reducing the temperature to 170 ℃, maintaining the temperature for 2 hours under 0.08MPa, sampling and measuring the acid value, wherein the acid value is 0.9mgKOH/g, and the negative pressure esterification reaction is finished; the temperature is reduced to 60 ℃, and discharging is carried out. To obtain the modified phthalic anhydride polyester polyol with a hydroxyl value of 225mgKOH/g and a viscosity of 2600mPa & s at 25 ℃.
(2) Preparation of polyurethane foams
Weighing 60g of polyether polyol according to the mass parts, mixing and stirring uniformly 40g of obtained modified phthalic anhydride polyester polyol, 2g of foam stabilizer, 0.7g of amine catalyst, 0.7g of potassium isooctanoate, 0.4g of potassium acetate, 2.5g of water and 12g of cyclopentane to prepare composite polyether, wherein the foam stabilizer is dimethyl siloxane, and the amine catalyst is N, N-dimethyl cyclohexylamine; mechanically stirring the combined polyether with the mass ratio of 1:1.5 and the multi-time methyl polyphenyl polyisocyanate for 10s at the rotating speed of 10000r/min to prepare the polyurethane foam.
Example 2
(1) Preparation of modified phthalic anhydride polyester polyol
Installing a reflux condenser pipe on a four-neck flask, adding diethylene glycol, heating to 110 ℃ under stirring, then adding phthalic anhydride, isoprene glycol and a catalyst of tetraisopropyl titanate, introducing nitrogen, distilling off water when the temperature is increased to 180 ℃, starting normal-pressure esterification reaction, heating at a heating rate of 10 ℃/h, heating to 230 ℃, controlling the temperature above the normal-pressure esterification reaction to be 90 ℃ in the heating process, maintaining for 2 hours at 230 ℃, sampling and measuring the acid value when the temperature is reduced to 55 ℃ when the temperature is reduced, wherein the acid value is 9mgKOH/g, and the normal-pressure esterification reaction is finished; reducing the temperature to 170 ℃, maintaining the temperature for 2.1 hours under 0.08MPa, sampling and measuring the acid value, wherein the acid value is 0.8mgKOH/g, and the negative pressure esterification reaction is finished; the temperature is reduced to 60 ℃, and discharging is carried out. To obtain the modified phthalic anhydride polyester polyol with a hydroxyl value of 230mgKOH/g and a viscosity of 2500mPa & s at 25 ℃.
(2) Preparation of polyurethane foams
Weighing 60g of polyether polyol according to the mass parts, mixing and stirring uniformly 40g of obtained modified phthalic anhydride polyester polyol, 2g of foam stabilizer, 0.7g of amine catalyst, 0.7g of potassium isooctanoate, 0.4g of potassium acetate, 2.5g of water and 12g of cyclopentane to prepare composite polyether, wherein the foam stabilizer is dimethyl siloxane, and the amine catalyst is N, N-dimethyl cyclohexylamine; mechanically stirring the combined polyether with the mass ratio of 1:1.5 and the multi-time methyl polyphenyl polyisocyanate for 10s at the rotating speed of 10000r/min to prepare the polyurethane foam.
Example 3
(1) Preparation of modified phthalic anhydride polyester polyol
Installing a reflux condenser pipe on a four-neck flask, adding diethylene glycol, heating to 110 ℃ under stirring, then adding phthalic anhydride, 1, 2-octanediol and a catalyst of tetraisopropyl titanate, introducing nitrogen, distilling off water when the temperature is increased to 180 ℃, starting normal-pressure esterification reaction, heating at a heating rate of 10 ℃/h, increasing the temperature to 230 ℃, controlling the temperature above the normal-pressure esterification reaction to be 90 ℃ in the heating process, maintaining the temperature at 230 ℃ for 2 hours, reducing the temperature to 60 ℃, sampling and measuring the acid value, and finishing the normal-pressure esterification reaction when the acid value is 8.5 mgKOH/g; reducing the temperature to 170 ℃, maintaining the temperature for 2.1 hours under 0.08MPa, sampling and measuring the acid value, wherein the acid value is 0.72mgKOH/g, and the negative pressure esterification reaction is finished; the temperature is reduced to 60 ℃, and discharging is carried out. To obtain the modified phthalic anhydride polyester polyol with a hydroxyl value of 232mgKOH/g and a viscosity of 2530 mPas at 25 ℃.
(2) Preparation of polyurethane foams
Weighing 60g of polyether polyol according to the mass parts, mixing and stirring uniformly 40g of obtained modified phthalic anhydride polyester polyol, 2g of foam stabilizer, 0.7g of amine catalyst, 0.7g of potassium isooctanoate, 0.4g of potassium acetate, 2.5g of water and 12g of cyclopentane to prepare composite polyether, wherein the foam stabilizer is dimethyl siloxane, and the amine catalyst is N, N-dimethyl cyclohexylamine; mechanically stirring the combined polyether with the mass ratio of 1:1.5 and the multi-time methyl polyphenyl polyisocyanate for 10s at the rotating speed of 10000r/min to prepare the polyurethane foam.
Example 4
(1) Preparation of modified phthalic anhydride polyester polyol
Installing a reflux condenser pipe on a four-neck flask, adding diethylene glycol, heating to 120 ℃ under stirring, then adding phthalic anhydride, neopentyl glycol, isoprene glycol and a catalyst of tetraisopropyl titanate, introducing nitrogen, distilling off water when the temperature is increased to 180 ℃, starting normal pressure esterification reaction, heating at a heating rate of 10 ℃/h, heating to 250 ℃, controlling the temperature above the normal pressure esterification reaction to be 90 ℃ in the heating process, maintaining the temperature at 250 ℃ for 1 hour, reducing the temperature to 55 ℃, sampling and measuring the acid value, wherein the acid value is 9.5mgKOH/g, and completing the normal pressure esterification reaction; reducing the temperature to 170 ℃, maintaining the temperature for 4 hours under 0.05MPa, sampling and measuring the acid value, wherein the acid value is 0.83mgKOH/g, and the negative pressure esterification reaction is finished; the temperature is reduced to 80 ℃, and the material is discharged. The modified phthalic anhydride polyester polyol is obtained, the hydroxyl value is 237mgKOH/g, and the viscosity at 25 ℃ is 2730mPa & s.
(2) Preparation of polyurethane foams
Weighing 55g of polyether polyol according to the mass parts, mixing and stirring 45g of obtained modified phthalic anhydride polyester polyol, 3g of foam stabilizer, 1.2g of amine catalyst, 1g of potassium isooctanoate, 0.6g of potassium acetate, 3g of water and 14g of cyclopentane uniformly to prepare composite polyether, wherein the foam stabilizer is dimethyl siloxane, and the amine catalyst is N, N-dimethyl cyclohexylamine; mechanically stirring the combined polyether with the mass ratio of 0.9:1.5 and the multi-time methyl polyphenyl polyisocyanate for 10s under the condition of the rotating speed of 10000r/min to prepare the polyurethane foam.
Example 5
(1) Preparation of modified phthalic anhydride polyester polyol
Installing a reflux condenser pipe on a four-neck flask, adding diethylene glycol, heating to 100 ℃ under stirring, then adding phthalic anhydride, neopentyl glycol and a catalyst of tetraisopropyl titanate, introducing nitrogen, distilling off water when the temperature is increased to 180 ℃, starting normal-pressure esterification reaction, heating at a heating rate of 10 ℃/h, heating to 230 ℃, controlling the temperature above the normal-pressure esterification reaction to be 90 ℃ in the heating process, maintaining for 2 hours at 230 ℃, reducing the temperature to 55 ℃, sampling and measuring the acid value, wherein the acid value is 9.6mgKOH/g, and completing the normal-pressure esterification reaction; reducing the temperature to 210 ℃, maintaining the temperature for 2 hours under 0.09MPa, sampling and measuring the acid value, wherein the acid value is 0.92mgKOH/g, and the negative pressure esterification reaction is finished; the temperature is reduced to 60 ℃, and discharging is carried out. To obtain the modified phthalic anhydride polyester polyol with a hydroxyl value of 235mgKOH/g and a viscosity of 2470mPa & s at 25 ℃.
(2) Preparation of polyurethane foams
Weighing 60g of polyether polyol according to the mass parts, mixing and stirring uniformly 40g of obtained modified phthalic anhydride polyester polyol, 2g of foam stabilizer, 0.7g of amine catalyst, 0.7g of potassium isooctanoate, 0.4g of potassium acetate, 2.5g of water and 12g of cyclopentane to prepare composite polyether, wherein the foam stabilizer is dimethyl siloxane, and the amine catalyst is N, N-dimethyl cyclohexylamine; mechanically stirring the combined polyether with the mass ratio of 1:1.2 and the multi-time methyl polyphenyl polyisocyanate for 10s at the rotating speed of 10000r/min to prepare the polyurethane foam.
Comparative example 1
(1) Preparation of phthalic anhydride polyester polyol
Installing a reflux condenser pipe on a four-neck flask, adding 430g of diethylene glycol, heating to 110 ℃ under stirring, then adding 210g of phthalic anhydride and 0.17g of catalyst tetraisopropyl titanate, introducing nitrogen, distilling off water when the temperature is increased to 180 ℃, starting normal-pressure esterification reaction, heating at a heating rate of 10 ℃/h, heating to 230 ℃, controlling the temperature above the normal-pressure esterification reaction to be 90 ℃ in the heating process, maintaining the temperature at 230 ℃ for 2 hours, reducing the temperature to 55 ℃, sampling and measuring the acid value, wherein the acid value is 9.1mgKOH/g, and the normal-pressure esterification reaction is finished; reducing the temperature to 170 ℃, maintaining the temperature for 2 hours under 0.08MPa, sampling and measuring the acid value, wherein the acid value is 0.83mgKOH/g, and the negative pressure esterification reaction is finished; the temperature is reduced to 60 ℃, and discharging is carried out. To obtain phthalic anhydride polyester polyol with a hydroxyl value of 250mgKOH/g and a viscosity of 2800 mPas at 25 ℃.
(2) Preparation of polyurethane foams
Weighing 60g of polyether polyol, 40g of phthalic anhydride polyester polyol, 2g of foam stabilizer, 0.7g of amine catalyst, 0.7g of potassium isooctanoate, 0.4g of potassium acetate, 2.5g of water and 12g of cyclopentane according to the mass parts, uniformly mixing and stirring to prepare the composite polyether, and obviously layering the composite polyether after 5 minutes. Mechanically stirring the combined polyether with the mass ratio of 1:1.5 and the multi-time methyl polyphenyl polyisocyanate for 10s at the rotating speed of 10000r/min to prepare the polyurethane foam.
As can be seen from the table, the modified phthalic anhydride polyester polyol prepared by the formula has low viscosity, high activity and good compatibility with cyclopentane. The modified phthalic anhydride polyester polyol is applied to polyurethane foam, and the obtained polyurethane foam has high overall density, high apparent core density, high compressive strength and good low-temperature dimensional stability.
Claims (7)
1. The composite polyether is characterized by comprising the following components in parts by mass: 40-45 parts of modified phthalic anhydride polyester polyol, 55-60 parts of polyether polyol, 2-3 parts of foam stabilizer, 0.7-1.2 parts of amine catalyst, 1.1-1.6 parts of metal catalyst, 2.5-3 parts of water and 12-14 parts of cyclopentane; the metal catalyst comprises 0.7-1 part of potassium isooctanoate and 0.4-0.6 part of potassium acetate;
the modified phthalic anhydride polyester polyol has an acid value of not more than 1.0mgKOH/g, a viscosity of 2000-4500 mPa & s at 25 ℃, and a hydroxyl value of 50-500 mgKOH/g, and is prepared by the following method:
(1) carrying out normal pressure esterification reaction on diethylene glycol, phthalic anhydride and alkane alcohol under the conditions of a catalyst and a protective atmosphere to obtain a mixture A;
(2) carrying out negative pressure polycondensation reaction on the obtained mixture A;
wherein the mass ratio of the diethylene glycol to the phthalic anhydride to the alkane alcohol is (4-6): (2-3): (0.02-0.03); the alkane alcohol is one or more of neopentyl glycol, isoprene glycol and 1, 2-octanediol; the normal pressure esterification reaction comprises a heating process and a heat preservation process; the temperature in the temperature rising process is 180-230 ℃, and the time in the temperature rising process is 5-7 hours; the heating rate in the heating process is 8-12 ℃/h; the temperature in the heat preservation process is 230-250 ℃, and the time in the heat preservation process is 1-2 h;
controlling the temperature above the esterification reaction not to exceed 100 ℃;
the acid value of the mixture A is less than or equal to 10 mgKOH/g;
the temperature of the negative pressure polycondensation reaction is 180-200 ℃; the time of the negative pressure polycondensation reaction is 2.1-4 h; the vacuum degree of the negative pressure polycondensation reaction is 0.05-0.09 MPa;
and after the negative pressure polycondensation reaction, cooling to 60-80 ℃, and then discharging.
2. The composite polyether of claim 1, wherein prior to the atmospheric esterification reaction, the diethylene glycol is heated to 100 to 120 ℃ and then mixed with the phthalic anhydride and the alkane alcohol;
the mass ratio of the diethylene glycol to the catalyst is (4-6): (0.0001 to 0.003);
the catalyst is one or more of n-butyl titanate, isopropyl titanate, tetra (2-ethyl hexanol) titanium and tetraisooctyl titanate;
the protective atmosphere is a nitrogen atmosphere.
3. The conjugate polyether of claim 1, wherein the modified phthalic anhydride polyester polyol has an acid value of 0.92mgKOH/g or less; the viscosity of the modified phthalic anhydride polyester polyol at 25 ℃ is 2470-2730 mPa & s; the hydroxyl value of the modified phthalic anhydride polyester polyol is 200-250 mgKOH/g.
4. A method for preparing the composite polyether as claimed in any one of claims 1 to 3, wherein the components are stirred and mixed.
5. A polyurethane foam raw material composition is characterized by comprising the following components: a conjugate polyether and a polymethine polyphenyl polyisocyanate as defined in claim 1; the mass ratio of the combined polyether to the polymethine polyphenyl polyisocyanate is (0.9-1): (1.2-1.5).
6. A preparation method of polyurethane foam is characterized by comprising the following steps: mixing the conjugate polyether of claim 5 and the polymethine polyphenyl polyisocyanate; the mixing is carried out by stirring, the rotating speed of the stirring is 8000-10000 r/min, and the stirring time is 8-12 s.
7. A polyurethane foam produced by the production method according to claim 6.
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| CN1803878A (en) * | 2005-12-22 | 2006-07-19 | 辽阳东辰聚氨酯有限公司 | Polyester polyol for preparation of polyurethane foam, polyisocyanurate foam and polyurethane adhesive and preparation process thereof |
| CN102115528A (en) * | 2009-12-31 | 2011-07-06 | 浙江华峰新材料股份有限公司 | Aromatic polyester polyol for improving compatibility of hydrocarbon blowing agent and preparation method thereof |
| US20160002386A1 (en) * | 2013-03-15 | 2016-01-07 | Stepan Company | Polyester polyols imparting improved flammability properties |
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| CN1803878A (en) * | 2005-12-22 | 2006-07-19 | 辽阳东辰聚氨酯有限公司 | Polyester polyol for preparation of polyurethane foam, polyisocyanurate foam and polyurethane adhesive and preparation process thereof |
| CN102115528A (en) * | 2009-12-31 | 2011-07-06 | 浙江华峰新材料股份有限公司 | Aromatic polyester polyol for improving compatibility of hydrocarbon blowing agent and preparation method thereof |
| US20160002386A1 (en) * | 2013-03-15 | 2016-01-07 | Stepan Company | Polyester polyols imparting improved flammability properties |
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