CN108690185A - Modified benzoic anhydride polyester polyol, combined polyether, polyurethane foam feedstock composition, polyurethane foam and preparation method thereof - Google Patents
Modified benzoic anhydride polyester polyol, combined polyether, polyurethane foam feedstock composition, polyurethane foam and preparation method thereof Download PDFInfo
- Publication number
- CN108690185A CN108690185A CN201710229744.4A CN201710229744A CN108690185A CN 108690185 A CN108690185 A CN 108690185A CN 201710229744 A CN201710229744 A CN 201710229744A CN 108690185 A CN108690185 A CN 108690185A
- Authority
- CN
- China
- Prior art keywords
- temperature
- polyurethane foam
- polyester polyol
- preparation
- pressure esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 46
- 229920000570 polyether Polymers 0.000 title claims abstract description 44
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 42
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 40
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 39
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical class C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 293
- 238000005886 esterification reaction Methods 0.000 claims abstract description 54
- 230000032050 esterification Effects 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- -1 ester polyol Chemical class 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 10
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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
- 239000002253 acid Substances 0.000 claims description 40
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 13
- 229920001228 polyisocyanate Polymers 0.000 claims description 13
- 239000005056 polyisocyanate Substances 0.000 claims description 13
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- 150000003077 polyols Chemical class 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 235000011056 potassium acetate Nutrition 0.000 claims description 8
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000004872 foam stabilizing agent Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000004321 preservation 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 7
- 206010000269 abscess Diseases 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000006260 foam Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 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 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 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
Landscapes
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A kind of modified benzoic anhydride polyester polyol of present invention offer, combined polyether, polyurethane foam feedstock composition, polyurethane foam and preparation method thereof.The preparation method of modified benzoic anhydride polyester polyol:Diethylene glycol (DEG), phthalic anhydride and alkanes alcohol carry out normal pressure esterification reaction, negative pressure esterification successively under catalyst and protective atmosphere;Wherein, the mass ratio of diethylene glycol (DEG), phthalic anhydride and alkanes alcohol is (4~6):(2~3):(0.02~0.03);Alkanes alcohol is one or more in neopentyl glycol, isoprene and 1,2- ethohexadiols;The temperature of normal pressure esterification reaction, time are respectively 180~250 DEG C, 7~8h;The temperature of negative pressure esterification, time are respectively 170~210 DEG C, 2~4h.The compatibility of gained modified aromatic adoption ester polyol and pentane is good, and the abscess of gained polyurethane foam is fine and smooth, hardness is good, stable structure, shrinking percentage is low, heat insulation effect is good, anti-flammability is excellent.
Description
Technical field
The present invention relates to a kind of modified benzoic anhydride polyester polyol, combined polyether, polyurethane foam feedstock composition, polyurethane
Foam and preparation method thereof.
Background technology
Hard polyurethane foams (abbreviation hard polyurethane foam) are used extensively because its superior performance, molding are simple, easy for construction
Make various adiabatic, shockproof, acoustic materials, light structures part and packaging material etc..It is well known that preparing the more of polyurethane foam
First alcohol is broadly divided into polyether polyol and polyester polyol, and polyester polyol is divided into aliphatic polyester polyols and aromatic polyester
Polyalcohol.But due to introducing phenyl ring in molecular structure in aromatic polyester polyol, had by its polyurethane foam obtained
There are the advantages such as intensity height, good toughness, anti-flammability be excellent, therefore is increasingly taken seriously.Currently, domestic aromatic polyester polyol is big
Mostly use phthalic anhydride, diethylene glycol (DEG) for raw material prepare, it is poor with the compatibility of physical blowing agent, and current era physical blowing agent with
Based on pentane, so the application of aromatic polyester polyol is restricted.
Invention content
The technical problem to be solved by the present invention is in order to overcome, aromatic polyester polyol and physics are sent out in the prior art
The poor defect of the compatibility of infusion pentane, and provide a kind of with the preferably modified benzoic anhydride polyester polyol of pentane compatibility, group
Close polyethers, polyurethane foam feedstock composition, polyurethane foam and preparation method thereof.Modified aromatic adoption ester polyol and pentane
Compatibility it is good, the abscess of gained polyurethane foam is fine and smooth, hardness is good, stable structure, shrinking percentage is low, heat insulation effect is good, fire-retardant
Property is excellent.
The present invention provides a kind of preparation method of modified benzoic anhydride polyester polyol comprising following steps:
(1) diethylene glycol (DEG), phthalic anhydride and alkanes alcohol after carrying out normal pressure esterification reaction, obtain mixed under catalyst and protective atmosphere
Close object A;
(2) gained mixture A is subjected to negative pressure esterification, you can;
Wherein, the mass ratio of the diethylene glycol (DEG), phthalic anhydride and alkanes alcohol is (4~6):(2~3):(0.02~0.03);Institute
It is one or more in neopentyl glycol, isoprene and 1,2- ethohexadiols to state alkanes alcohol;The temperature of the normal pressure esterification reaction
Degree is 180~250 DEG C, and the time of the normal pressure esterification reaction is 7~8h;The temperature of the negative pressure esterification is 170~210
DEG C, the time of the negative pressure esterification is 2~4h.
In the present invention, before the normal pressure esterification reaction, the diethylene glycol (DEG) is first preferably heated to 100~120 DEG C, example
It such as can be 110 DEG C, then be mixed with the phthalic anhydride and the alkanes alcohol.
In the present invention, the dosage of the catalyst can be that this field is conventional, the quality of the diethylene glycol (DEG) and the catalyst
Than preferably (4~6):(0.0001~0.003).
In the present invention, the catalyst be esterification class catalyst commonly used in the art, preferably tetrabutyl titanate,
It is one or more in four different monooctyl ester of isopropyl titanate, four (2-ethylhexanol) titaniums and metatitanic acid, more preferably for tetrabutyl titanate and/
Or isopropyl titanate.
In the present invention, the protective atmosphere is protective atmosphere commonly used in the art, preferably nitrogen atmosphere.
In the present invention, the normal pressure esterification reaction is preferably comprised temperature-rise period and insulating process.Wherein, described to heat up
The temperature of journey is preferably 180~250 DEG C, is more preferably 180~230 DEG C, and time of the temperature-rise period is preferably 5~
The heating rate of 7h, the temperature-rise period are preferably 8~12 DEG C/h, may be, for example, 10 DEG C/h.The temperature of the insulating process
Preferably 230~250 DEG C, the time of the insulating process is preferably 1~2h.
In the present invention, during the normal pressure esterification reaction carries out, there is water to distillate, to make the flat of the normal pressure esterification reaction
It is steady to carry out, it preferably controls the temperature above the esterification and is no more than 100 DEG C, may be, for example, 90 DEG C.
In the present invention, the acid value of the mixture A preferably≤10mgKOH/g, may be, for example, 8mgKOH/g,
8.5mgKOH/g, 9mgKOH/g, 9.5mgKOH/g or 9.6mgKOH/g.The measurement of the acid value is preferably in the esterification
The temperature of top is down at 55~60 DEG C and is carried out.
In the present invention, the temperature of the negative pressure esterification is preferably 180~200 DEG C.The negative pressure esterification
Time is preferably 2.1~4h.The vacuum degree of the negative pressure esterification is preferably 0.05~0.09MPa, may be, for example,
0.08MPa。
In the present invention, after the negative pressure esterification, after being preferably cooled to 60~100 DEG C, then blowing is carried out;More preferably
After being cooled to 60~80 DEG C, then carry out blowing.
The present invention also provides one kind, and modified benzoic anhydride polyester polyol, the modified phthalic anhydride made from above-mentioned preparation method are poly-
Acid value≤1.0mgKOH/g of ester polyol, viscosity at 25 DEG C are 2000~4500mPas, hydroxyl value is 50~
500mgKOH/g。
In the present invention, the acid value of the modified benzoic anhydride polyester polyol preferably≤0.92mgKOH/g, may be, for example,
0.9mgKOH/g, 0.83mgKOH/g, 0.8mgKOH/g or 0.72mgKOH/g.
In the present invention, viscosity of the modified benzoic anhydride polyester polyol at 25 DEG C is preferably 2470~2730mPa
s。
In the present invention, the hydroxyl value of the modified benzoic anhydride polyester polyol is preferably 200~250mgKOH/g, may be, for example,
225mgKOH/g, 230mgKOH/g, 232mgKOH/g, 235mgKOH/g or 237mgKOH/g.
The present invention also provides a kind of combined polyether, the combined polyether includes each component of following mass fraction:40~45
Part modified benzoic anhydride polyester polyol, 55~60 parts of polyether polyol, 2~3 parts of foam stabilizers, 0.7~1.2 part of amines catalysis
Agent, 1.1~1.6 parts of metal-based catalysts, 2.5~3 parts of water and 12~14 parts of pentamethylene;The metal-based catalysts are 0.7~1
Part isooctyl acid potassium and 0.4~0.6 part of potassium acetate.
In the present invention, conventional use of modifying agent, such as soybean oil in this field are may also include in the combined polyether.It is described
It may also include conventional use of fire retardant in this field in combined polyether.
The present invention also provides the preparation method of the combined polyether, the preparation method of the polyethers routinely will according to this field
Above-mentioned each component is stirred mixing.
The present invention also provides a kind of polyurethane foam feedstock composition, the feedstock composition includes following component:It is described
Combined polyether and polymethine polyphenyl polyisocyanate.
In the present invention, the mass ratio of the combined polyether and the polymethine polyphenyl polyisocyanate is preferably
(0.9~1):(1.2~1.5).
The polyurethane foam feedstock composition of the present invention is before use, the combined polyether and the more benzene of the polymethine
Quito isocyanates is not in contact always, therefore the polyurethane foam feedstock composition is sold and preserved to the form that can be set with,
The combined polyether and the polymethine polyphenyl polyisocyanate are mixed when use, you can.
The present invention also provides a kind of preparation methods of polyurethane foam comprising following steps:By the combined polyether and
The polymethine polyphenyl polyisocyanate mixing.
In the present invention, preferably using stirring, the rotating speed of the stirring is preferably 8000~10000r/ for the mixing
The time of min, the stirring are preferably 8~12s, may be, for example, 10s.
The polyurethane foam made from above-mentioned preparation method that the present invention also provides one kind.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:Modified benzoic anhydride polyester polyol purity made from formula by the present invention
Height, viscosity are low, active high, good with pentamethylene compatibility.The modification benzoic anhydride polyester polyol is applied in polyurethane foam, institute
The abscess intensity height, hardness height, flame retardant property for obtaining polyurethane foam are good, and abscess is fine and smooth, mechanical property is good, and heat insulation effect is good.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
Following used raw materials of embodiment are commercially available.
In following embodiments, the viscosity that gained is modified benzoic anhydride polyester polyol is measured using rotational viscometer at 25 DEG C,
Design parameter is:No. 3 rotors, rotating speed 120r/min.
The mass ratio of raw material see the table below in following embodiments:
Embodiment 1
(1) preparation of modified benzoic anhydride polyester polyol
Reflux condensing tube is loaded onto in four-neck flask, and diethylene glycol (DEG) is added and is warming up to 110 DEG C under stiring, benzene is then added
Acid anhydride, neopentyl glycol and catalyst tetraisopropyl titanate, are passed through nitrogen, when temperature is raised to 180 DEG C, has water to distillate, proceed by
Normal pressure esterification reacts, and is heated up with the heating rate of 10 DEG C/h, temperature is risen to 230 DEG C, and normal pressure ester is controlled in temperature-rise period
The temperature for changing reaction top is 90 DEG C, is maintained 2 hours at 230 DEG C, and temperature is down to 55 DEG C, sampling detecting acid number, and acid value is
8mgKOH/g, normal pressure esterification reaction are completed;170 DEG C are cooled the temperature to, at 0.08MPa, is maintained 2 hours, sampling detecting acid number, acid
Value is 0.9mgKOH/g, and negative pressure esterification terminates;Temperature is down to 60 DEG C, discharging.Obtain modified benzoic anhydride polyester polyol, hydroxyl value
For 225mgKOH/g, 25 DEG C of viscosity are 2600mPas.
(2) preparation of polyurethane foam
Polyether polyol 60g is weighed according to mass parts, gained is modified benzoic anhydride polyester polyol 40g, foam stabilizer 2g, amine and urges
Agent 0.7g, isooctyl acid potassium 0.7g, potassium acetate 0.4g, water 2.5g, pentamethylene 12g are mixed evenly and combined polyether are made, institute
The foam stabilizer stated is dimethyl siloxane, and the amines catalyst is N, N- dimethyl cyclohexyl amines;It is 1 by mass ratio:1.5
Gained combined polyether and polymethine polyphenyl polyisocyanate mechanical agitation 10s under the conditions of rotating speed 10000r/min, are made
Polyurethane foam.
Embodiment 2
(1) preparation of modified benzoic anhydride polyester polyol
Reflux condensing tube is loaded onto in four-neck flask, and diethylene glycol (DEG) is added and is warming up to 110 DEG C under stiring, benzene is then added
Acid anhydride, isoprene and catalyst tetraisopropyl titanate, are passed through nitrogen, when temperature is raised to 180 DEG C, has water to distillate, proceed by
Normal pressure esterification reacts, and is heated up with the heating rate of 10 DEG C/h, temperature is risen to 230 DEG C, and normal pressure ester is controlled in temperature-rise period
The temperature for changing reaction top is 90 DEG C, maintains 2 hours at 230 DEG C, when temperature is begun to decline, when temperature is down to 55 DEG C, takes
Sample surveys acid value, acid value 9mgKOH/g, and normal pressure esterification reaction is completed;170 DEG C are cooled the temperature to, at 0.08MPa, maintains 2.1
Hour, sampling detecting acid number, acid value 0.8mgKOH/g, negative pressure esterification terminate;Temperature is down to 60 DEG C, discharging.It is modified
Benzoic anhydride polyester polyol, hydroxyl value 230mgKOH/g, 25 DEG C of viscosity are 2500mPas.
(2) preparation of polyurethane foam
Polyether polyol 60g is weighed according to mass parts, gained is modified benzoic anhydride polyester polyol 40g, foam stabilizer 2g, amine and urges
Agent 0.7g, isooctyl acid potassium 0.7g, potassium acetate 0.4g, water 2.5g, pentamethylene 12g are mixed evenly and combined polyether are made, institute
The foam stabilizer stated is dimethyl siloxane, and the amines catalyst is N, N- dimethyl cyclohexyl amines;It is 1 by mass ratio:1.5
Gained combined polyether and polymethine polyphenyl polyisocyanate mechanical agitation 10s under the conditions of rotating speed 10000r/min, are made
Polyurethane foam.
Embodiment 3
(1) preparation of modified benzoic anhydride polyester polyol
Reflux condensing tube is loaded onto in four-neck flask, and diethylene glycol (DEG) is added and is warming up to 110 DEG C under stiring, benzene is then added
Acid anhydride, 1,2- ethohexadiols and catalyst tetraisopropyl titanate, are passed through nitrogen, have water to distillate when temperature is raised to 180 DEG C, proceed by
Normal pressure esterification reacts, and is heated up with the heating rate of 10 DEG C/h, temperature is risen to 230 DEG C, and normal pressure ester is controlled in temperature-rise period
The temperature for changing reaction top is 90 DEG C, is maintained 2 hours at 230 DEG C, and temperature is down to 60 DEG C, sampling detecting acid number, and acid value is
When 8.5mgKOH/g, normal pressure esterification reaction is completed;170 DEG C are cooled the temperature to, at 0.08MPa, is maintained 2.1 hours, sampling is surveyed
Acid value, acid value 0.72mgKOH/g, negative pressure esterification terminate;Temperature is down to 60 DEG C, discharging.It is more to obtain modified phthalic anhydride polyester
First alcohol, hydroxyl value 232mgKOH/g, 25 DEG C of viscosity are 2530mPas.
(2) preparation of polyurethane foam
Polyether polyol 60g is weighed according to mass parts, gained is modified benzoic anhydride polyester polyol 40g, foam stabilizer 2g, amine and urges
Agent 0.7g, isooctyl acid potassium 0.7g, potassium acetate 0.4g, water 2.5g, pentamethylene 12g are mixed evenly and combined polyether are made, institute
The foam stabilizer stated is dimethyl siloxane, and the amines catalyst is N, N- dimethyl cyclohexyl amines;It is 1 by mass ratio:1.5
Gained combined polyether and polymethine polyphenyl polyisocyanate mechanical agitation 10s under the conditions of rotating speed 10000r/min, are made
Polyurethane foam.
Embodiment 4
(1) preparation of modified benzoic anhydride polyester polyol
Reflux condensing tube is loaded onto in four-neck flask, and diethylene glycol (DEG) is added and is warming up to 120 DEG C under stiring, benzene is then added
Acid anhydride, neopentyl glycol, isoprene and catalyst tetraisopropyl titanate, are passed through nitrogen, when temperature is raised to 180 DEG C, have water to distillate,
Normal pressure esterification reaction is proceeded by, is heated up with the heating rate of 10 DEG C/h, temperature is risen to 250 DEG C, is controlled in temperature-rise period
The temperature of normal pressure esterification reaction processed top is 90 DEG C, is maintained 1 hour at 250 DEG C, and temperature is down to 55 DEG C, and sampling detecting acid number is sour
Value is 9.5mgKOH/g, and normal pressure esterification reaction is completed;170 DEG C are cooled the temperature to, at 0.05MPa, is maintained 4 hours, sampling is surveyed
Acid value, acid value 0.83mgKOH/g, negative pressure esterification terminate;Temperature is down to 80 DEG C, discharging.It is more to obtain modified phthalic anhydride polyester
First alcohol, hydroxyl value 237mgKOH/g, 25 DEG C of viscosity are 2730mPas.
(2) preparation of polyurethane foam
Polyether polyol 55g is weighed according to mass parts, gained is modified benzoic anhydride polyester polyol 45g, foam stabilizer 3g, amine and urges
Agent 1.2g, isooctyl acid potassium 1g, potassium acetate 0.6g, water 3g, pentamethylene 14g are mixed evenly and combined polyether are made, described
Foam stabilizer is dimethyl siloxane, and the amines catalyst is N, N- dimethyl cyclohexyl amines;It is 0.9 by mass ratio:1.5 institute
Combined polyether and polymethine polyphenyl polyisocyanate mechanical agitation 10s under the conditions of rotating speed 10000r/min are obtained, is made poly-
Urethane foam.
Embodiment 5
(1) preparation of modified benzoic anhydride polyester polyol
Reflux condensing tube is loaded onto in four-neck flask, and diethylene glycol (DEG) is added and is warming up to 100 DEG C under stiring, benzene is then added
Acid anhydride, neopentyl glycol and catalyst tetraisopropyl titanate, are passed through nitrogen, when temperature is raised to 180 DEG C, has water to distillate, proceed by
Normal pressure esterification reacts, and is heated up with the heating rate of 10 DEG C/h, temperature is risen to 230 DEG C, and normal pressure ester is controlled in temperature-rise period
The temperature for changing reaction top is 90 DEG C, is maintained 2 hours at 230 DEG C, and temperature is down to 55 DEG C, sampling detecting acid number, and acid value is
9.6mgKOH/g, normal pressure esterification reaction are completed;210 DEG C are cooled the temperature to, at 0.09MPa, is maintained 2 hours, sampling detecting acid number,
Acid value is 0.92mgKOH/g, and negative pressure esterification terminates;Temperature is down to 60 DEG C, discharging.Modified benzoic anhydride polyester polyol is obtained,
Hydroxyl value is 235mgKOH/g, and 25 DEG C of viscosity are 2470mPas.
(2) preparation of polyurethane foam
Polyether polyol 60g is weighed according to mass parts, gained is modified benzoic anhydride polyester polyol 40g, foam stabilizer 2g, amine and urges
Agent 0.7g, isooctyl acid potassium 0.7g, potassium acetate 0.4g, water 2.5g, pentamethylene 12g are mixed evenly and combined polyether are made, institute
The foam stabilizer stated is dimethyl siloxane, and the amines catalyst is N, N- dimethyl cyclohexyl amines;It is 1 by mass ratio:1.2
Gained combined polyether and polymethine polyphenyl polyisocyanate mechanical agitation 10s under the conditions of rotating speed 10000r/min, are made
Polyurethane foam.
Comparative example 1
(1) preparation of benzoic anhydride polyester polyol
Reflux condensing tube is loaded onto in four-neck flask, and diethylene glycol (DEG) 430g is added and is warming up to 110 DEG C under stiring, then adds
Enter 210g phthalic anhydrides and 0.17g catalyst tetraisopropyl titanates, be passed through nitrogen, when temperature is raised to 180 DEG C, there is water to distillate, starts
Normal pressure esterification reaction is carried out, is heated up with the heating rate of 10 DEG C/h, temperature is risen to 230 DEG C, is controlled in temperature-rise period normal
It is 90 DEG C to press the temperature above esterification, is maintained 2 hours at 230 DEG C, and temperature is down to 55 DEG C, sampling detecting acid number, and acid value is
9.1mgKOH/g, normal pressure esterification reaction are completed;170 DEG C are cooled the temperature to, at 0.08MPa, is maintained 2 hours, sampling detecting acid number,
Acid value is 0.83mgKOH/g, and negative pressure esterification terminates;Temperature is down to 60 DEG C, discharging.Obtain benzoic anhydride polyester polyol, hydroxyl value
For 250mgKOH/g, 25 DEG C of viscosity are 2800mPas.
(2) preparation of polyurethane foam
Polyether polyol 60g, benzoic anhydride polyester polyol 40g, foam stabilizer 2g, amines catalyst are weighed according to mass fraction
0.7g, isooctyl acid potassium 0.7g, potassium acetate 0.4g, water 2.5g, pentamethylene 12g are mixed evenly and are configured to combined polyether, 5 minutes
Later combined polyether layering is apparent.It is 1 by mass ratio:1.5 gained combined polyether and polymethine polyphenyl polyisocyanate
Polyurethane foam is made in mechanical agitation 10s under the conditions of rotating speed 10000r/min.
As seen from the above table, modified benzoic anhydride polyester polyol viscosity made from formula of the invention is low, active high and pentamethylene
Compatibility is good.The modification benzoic anhydride polyester polyol is applied in polyurethane foam, the global density height of gained polyurethane foam,
Apparent core density height, compressive strength high and low temperature good stability of the dimension.
Claims (10)
1. a kind of preparation method of modified benzoic anhydride polyester polyol, which is characterized in that it includes the following steps:
(1) diethylene glycol (DEG), phthalic anhydride and alkanes alcohol after carrying out normal pressure esterification reaction, obtain mixture under catalyst and protective atmosphere
A;
(2) gained mixture A is subjected to negative pressure esterification, you can;
Wherein, the mass ratio of the diethylene glycol (DEG), phthalic anhydride and alkanes alcohol is (4~6):(2~3):(0.02~0.03);The alkane
Hydro carbons alcohol is one or more in neopentyl glycol, isoprene and 1,2- ethohexadiols;The temperature of normal pressure esterification reaction is
180~250 DEG C, the time of the normal pressure esterification reaction is 7~8h;The temperature of the negative pressure esterification is 170~210 DEG C,
The time of the negative pressure esterification is 2~4h.
2. preparation method as described in claim 1, which is characterized in that before the normal pressure esterification reaction, preferably first by institute
It states diethylene glycol (DEG) and is heated to 100~120 DEG C, then mixed with the phthalic anhydride and the alkanes alcohol;
The mass ratio of the diethylene glycol (DEG) and the catalyst is (4~6):(0.0001~0.003);
The catalyst is one kind in tetrabutyl titanate, four different monooctyl ester of isopropyl titanate, four (2-ethylhexanol) titaniums and metatitanic acid
Or a variety of, preferably tetrabutyl titanate and/or isopropyl titanate;
Alternatively, the protective atmosphere is nitrogen atmosphere.
3. preparation method as described in claim 1, which is characterized in that the normal pressure esterification reaction includes temperature-rise period and heat preservation
Process;The temperature of the temperature-rise period is 180~250 DEG C, and preferably 180~230 DEG C, the time of the temperature-rise period is 5
The heating rate of~7h, the temperature-rise period are 8~12 DEG C/h;The temperature of the insulating process is 230~250 DEG C, the guarantor
The time of warm process is 1~2h;
It controls the temperature above the esterification and is no more than 100 DEG C;
Alternatively, acid value≤10mgKOH/g of the mixture A.
4. preparation method as described in claim 1, which is characterized in that the temperature of the negative pressure esterification is 180~200
℃;The time of the negative pressure esterification is 2.1~4h;The vacuum degree of the negative pressure esterification is 0.05~0.09MPa;
After the negative pressure esterification, after being cooled to 60~100 DEG C, then blowing is carried out;After being preferably cooled to 60~80 DEG C, then
Carry out blowing.
5. one kind modified benzoic anhydride polyester polyol, feature as made from Claims 1 to 4 any one of them preparation method exist
In, acid value≤1.0mgKOH/g of the modified benzoic anhydride polyester polyol, the viscosity at 25 DEG C is 2000~4500mPas,
Hydroxyl value is 50~500mgKOH/g;The acid value of the modified benzoic anhydride polyester polyol preferably≤0.92mgKOH/g;The modification
Viscosity of the benzoic anhydride polyester polyol at 25 DEG C is preferably 2470~2730mPas;The modified benzoic anhydride polyester polyol
Hydroxyl value is preferably 200~250mgKOH/g.
6. a kind of combined polyether, which is characterized in that the combined polyether includes each component of following mass fraction:40~45 parts such as
Modification benzoic anhydride polyester polyol, 55~60 parts of polyether polyol, 2~3 parts of foam stabilizers described in claim 5,0.7~1.2 part
Amines catalyst, 1.1~1.6 parts of metal-based catalysts, 2.5~3 parts of water and 12~14 parts of pentamethylene;The metal-based catalysts
For 0.7~1 part of isooctyl acid potassium and 0.4~0.6 part of potassium acetate.
7. a kind of preparation method of combined polyether as claimed in claim 6, which is characterized in that by each group in claim 6
Divide and is stirred mixing.
8. a kind of polyurethane foam feedstock composition, which is characterized in that the feedstock composition includes following component:As right is wanted
Seek the combined polyether and polymethine polyphenyl polyisocyanate described in 6;The combined polyether and the more phenyl of the polymethine
The mass ratio of polyisocyanates is preferably (0.9~1):(1.2~1.5).
9. a kind of preparation method of polyurethane foam, which is characterized in that it includes the following steps:It will be as claimed in claim 6
Combined polyether and polymethine polyphenyl polyisocyanate mixing;The mixing is described to stir preferably using stirring
The rotating speed mixed is preferably 8000~10000r/min, and the time of the stirring is preferably 8~12s.
10. a kind of polyurethane foam, which is characterized in that the polyurethane foam is made by the preparation method described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710229744.4A CN108690185B (en) | 2017-04-10 | 2017-04-10 | Modified phthalic anhydride polyester polyol, composite polyether, polyurethane foam raw material composition, polyurethane foam and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710229744.4A CN108690185B (en) | 2017-04-10 | 2017-04-10 | Modified phthalic anhydride polyester polyol, composite polyether, polyurethane foam raw material composition, polyurethane foam and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108690185A true CN108690185A (en) | 2018-10-23 |
| CN108690185B CN108690185B (en) | 2021-02-26 |
Family
ID=63842288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710229744.4A Expired - Fee Related CN108690185B (en) | 2017-04-10 | 2017-04-10 | Modified phthalic anhydride polyester polyol, composite polyether, polyurethane foam raw material composition, polyurethane foam and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108690185B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627746A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of frangible formula protection cap in big negative pressure polyurethane front end and its forming method |
| CN110698659A (en) * | 2019-10-21 | 2020-01-17 | 万华化学集团股份有限公司 | Phthalic anhydride polyester polyol and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-04-10 CN CN201710229744.4A patent/CN108690185B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627746A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of frangible formula protection cap in big negative pressure polyurethane front end and its forming method |
| CN109627746B (en) * | 2018-11-23 | 2021-04-06 | 贵州航天天马机电科技有限公司 | Large negative pressure polyurethane front end fragile protective cover and forming method thereof |
| CN110698659A (en) * | 2019-10-21 | 2020-01-17 | 万华化学集团股份有限公司 | Phthalic anhydride polyester polyol and preparation method thereof |
| CN110698659B (en) * | 2019-10-21 | 2022-04-22 | 万华化学集团股份有限公司 | Phthalic anhydride polyester polyol and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108690185B (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102115528B (en) | Aromatic polyester polyol for improving compatibility of hydrocarbon blowing agent and preparation method thereof | |
| EP1086159B1 (en) | Aromatic polyester polyols made from a natural oil | |
| CN102947362B (en) | Foam insulation unit | |
| CN104448272B (en) | A kind of aromatic series high flame retardant PEPA and its production and use | |
| CN102532460A (en) | Bio-based polyurethane microporous elastomer, preparation method and application thereof | |
| CN110054752A (en) | A kind of low density rigid polyurethane foam and preparation method thereof | |
| CN108690185A (en) | Modified benzoic anhydride polyester polyol, combined polyether, polyurethane foam feedstock composition, polyurethane foam and preparation method thereof | |
| CN108383968A (en) | High heat conduction polyurethane solid-solid phase transition material and preparation method thereof | |
| JPS63172763A (en) | Viscosity reducing agent for aromatic polyester polyol and polyether polyol | |
| CN104829835B (en) | Preparation method of isocyanate-based polyimide foam | |
| JP3475763B2 (en) | Insulated box for refrigerator | |
| CN103030763B (en) | Polyimide modified polyisocyanurate foam and preparation method thereof | |
| CN105555850A (en) | Polyester polyol and polyol blends and rigid polyurethane foam manufacturing | |
| CN110407992A (en) | A kind of the material preparation and application of flame retardant polyurethane rigid foam | |
| CN113004510B (en) | Amino polyether polyol, preparation method thereof, polyurethane rigid foam prepared from amino polyether polyol and preparation method of polyurethane rigid foam | |
| CN110540626B (en) | Ultra-light macroporous reticular polyurethane foam plastic and ultra-low temperature preparation method thereof | |
| CN113174034A (en) | Polyester polyol and preparation method thereof | |
| JP2015083692A (en) | Polyol compositions, resin blend compositions, spray compositions, and methods of using each, and methods of making each | |
| CN108690187A (en) | Aromatic polyester polyol, feedstock composition, polyurethane foam and preparation method | |
| JP5043284B2 (en) | Method for producing polyester polyol | |
| JP2001172359A (en) | Preparation process for rigid polyurethane foam | |
| JP4265264B2 (en) | Method for producing polyester polyol | |
| KR102548562B1 (en) | Insulating materials for refrigeration system including rigid polyurethane foams made using polyol initiated by meta-toluenediamine | |
| JP4265265B2 (en) | Method for producing polyester polyol | |
| JP4178390B2 (en) | Rigid polyurethane foam molding composition and method for producing rigid polyurethane foam using the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210226 |