CN113621128A - Safety phenolic resin modified polyurethane functional material and preparation method thereof - Google Patents
Safety phenolic resin modified polyurethane functional material and preparation method thereof Download PDFInfo
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- CN113621128A CN113621128A CN202110937330.3A CN202110937330A CN113621128A CN 113621128 A CN113621128 A CN 113621128A CN 202110937330 A CN202110937330 A CN 202110937330A CN 113621128 A CN113621128 A CN 113621128A
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- phenolic resin
- functional material
- isocyanate
- modified polyurethane
- component
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 59
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 37
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 31
- 239000004814 polyurethane Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000012948 isocyanate Substances 0.000 claims abstract description 35
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 8
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004677 Nylon Substances 0.000 claims description 10
- 229920001778 nylon Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012973 diazabicyclooctane Substances 0.000 claims description 9
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 150000004702 methyl esters Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005829 trimerization reaction Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920003225 polyurethane elastomer Polymers 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 102100035474 DNA polymerase kappa Human genes 0.000 description 2
- 101710108091 DNA polymerase kappa Proteins 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 aliphatic hydroxyl compound Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WYWUBDZUGFHUML-UHFFFAOYSA-N butanedioic acid dimethyl butanedioate Chemical compound OC(=O)CCC(O)=O.COC(=O)CCC(=O)OC WYWUBDZUGFHUML-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
-
- 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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/54—Polycondensates of aldehydes
- C08G18/542—Polycondensates of aldehydes with phenols
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
Abstract
The invention relates to a safety type phenolic resin modified polyurethane functional material and a preparation method thereof, belonging to the technical field of polyurethane. The safe phenolic resin modified polyurethane functional material consists of a component A and a component B, wherein the component A comprises polyether polyol, a plasticizer, a flame retardant, a catalyst and an antioxidant, and the component B comprises isocyanate A, isocyanate B, solid phenolic resin and a solvent. The phenolic resin is first-order thermosetting phenolic resin without a curing agent, contains active group hydroxymethyl, and has a softening point of 80-100 ℃. The safety type phenolic resin modified polyurethane functional material has high toughness strength and rigidity and high flame retardant property; the invention also provides a simple and feasible preparation method.
Description
Technical Field
The invention relates to a safety type phenolic resin modified polyurethane functional material and a preparation method thereof, belonging to the technical field of polyurethane.
Background
Polyurethane as a high molecular compound has been widely used in many fields such as household appliances, buildings, daily necessities, traffic, etc. because of its good mechanical properties, easy processing, and simple operation. In recent years, with the continuous development of the field of new materials, higher requirements are put forward on the performance of the existing materials, and people hope to modify various materials which are relatively mature at present through technical means such as compounding, doping, grafting and the like, so that the performance of the existing materials is further improved, and the defects of a single type of materials in some aspects can be made up.
The polyurethane elastomer is one of polyurethane materials, and after years of development, with the continuous maturity of technology, the polyurethane elastomer is widely applied to a plurality of fields, but inevitably has some defects, for example, although the material has high toughness and strength, the material has insufficient rigidity, and has large deformation when being subjected to certain pressure; in addition, one of the main raw materials of the polyurethane material, polyether polyol, is mostly an aliphatic hydroxyl compound, so that the flame retardant performance of the material is poor, the oxygen index is low, the application range is limited to a certain extent, the defects of the polyurethane elastomer can be overcome, the performance of the polyurethane elastomer is further improved, the precondition for expanding the application range is provided, and a new research direction and a new subject are provided for workers in the material field and the polyurethane industry.
CN 201410717216.X discloses a phenolic resin modified rigid polyurethane foam and a preparation method thereof, wherein a self-made liquid phenolic resin is simultaneously mixed with isocyanate, polyether polyol, a foaming agent, a flame retardant and the like and then reacted to generate a foam material. However, it has the following problems: on one hand, the viscosity and the reaction degree of the liquid phenolic resin are not easy to control; on the other hand, the isocyanate, the phenolic resin, the polyether polyol and the like are simultaneously mixed and reacted, so that the rigid benzene rings in the phenolic resin cannot be uniformly distributed in reactants, the performance of products is unstable, the performances of different positions of foams are uneven, and the uniform mixing degree of materials has higher requirements on production process equipment and the like.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a safe phenolic resin modified polyurethane functional material which not only has higher toughness strength and rigidity, but also has higher flame retardant property; the invention also provides a simple and feasible preparation method.
The safe phenolic resin modified polyurethane functional material consists of a component A and a component B, wherein the component A comprises polyether polyol, a plasticizer, a flame retardant, a catalyst and an antioxidant, and the component B comprises isocyanate A, isocyanate B, solid phenolic resin and a solvent.
The phenolic resin is first-order thermosetting phenolic resin without a curing agent, contains active group hydroxymethyl, and has a softening point of 80-100 ℃.
The phenolic resin is divided into two categories of thermosetting and thermoplastic, wherein the thermosetting phenolic resin is not softened again along with the rise of temperature after being cured at high temperature, the addition reaction degree of the first-order thermosetting phenolic resin is greater than the polymerization reaction degree, the structure contains a large amount of active group hydroxymethyl, and the hydroxymethyl active group can react with isocyanic acid radical to generate carbamate group, so that a rigid aromatic ring in the phenolic resin is introduced into a polyurethane system, and the mechanical property and the flame retardant property of the phenolic resin are further improved. The preferred resins of the present invention are the HK-D6811 and HK-D6812 brand of Jining HuaKa resin, Inc.
Preferably, the polyether polyol has a functionality of 3, a hydroxyl value of 330 to 470mgKOH/g, and a relative molecular weight of 350 to 510. Further preferably one or more of DV125, MN-500 or MN-700 from Shandong Lanxingdong GmbH, and still more preferably MN-500.
Preferably, the plasticizer is one or more of dibutyl phthalate, dioctyl terephthalate, or diisononyl phthalate.
The catalyst is an organic tin catalyst and a trimerization catalyst which are used in a composite mode, and the further preferable composite proportion is 0.3: 0.2-1.0: 0.5.
Preferably, the organotin catalyst is T-12, T-120 or T-125.
Preferably, the trimerization catalyst is DABCO TMR, DABCO TMR-2, DABCO TMR-30, Polycat 41 or Polycat 46.
Preferably, the antioxidant is 245, 1790 or GA 80.
Preferably, the isocyanate A is polymeric MDI, the-NCO content of the isocyanate A is 30.5-32.0%, and the viscosity of the isocyanate A is 150-250 mPas; and the isocyanate B is MDI-50. Further preferably, the isocyanate A is PM-200 of Wanhua chemical group, Inc., and the isocyanate B is MDI-50 of Wanhua chemical group, Inc.
Preferably, the solvent is one or more of N, N-dimethylformamide, methyl nylon acid, N-methylpyrrolidone, tetrahydrofuran or carbon tetrachloride. More preferably methyl nylon carboxylate.
The nylon acid methyl ester is prepared from succinic acid (succinic acid) dimethyl ester CH3OOC(CH2)2COOCH3Dimethyl glutarate CH3OOC(CH2)3COOCH3And adipic acid dimethyl ester CH3OOC(CH2)4COOCH is composed of three dibasic acid ester solvents, is a high-boiling-point environment-friendly solvent which is nontoxic, colorless and has super strong dissolving capacity, and is a biodegradable environment-friendly high-boiling-point solvent. The phenolic resin is used as a resin material with a high polymer having a large number of benzene ring structures, a common solvent is not ideal for the dissolving effect of the phenolic resin, only an alcohol solvent is relatively good in effect, the methanol and ethanol effect is most ideal, but the alcohol solvent can generate different degrees of damage to human bodies on one hand, and on the other hand, the alcohol solvent has low flash point, is inflammable and the like, and brings great potential safety hazards in many fields, so that the phenolic resin is avoided to be used as much as possible.
The preparation method of the safe phenolic resin modified polyurethane functional material comprises the following steps:
(1) replacing the prepolymerization kettle B with nitrogen for three times, adding the solid phenolic resin, isocyanate B and solvent according to the formula ratio, starting stirring, heating to 60-80 ℃, reacting for 4-8 h, and cooling to room temperature after the-NCO content in the system reaches a target value to obtain a phenolic resin and isocyanate prepolymer;
(2) transferring the prepolymer in the step (1) to a mixing kettle B, adding isocyanate A according to the formula amount, and stirring to obtain a component B;
(3) putting polyether polyol, a plasticizer, a flame retardant, a catalyst and an antioxidant into a mixing kettle A according to the formula amount, and stirring to obtain a component A;
(4) according to the application and the using method, the using amount of the catalyst is adjusted, A, B components are mixed according to the calculated proportion when the catalyst is used, the mixture is poured into a mould or coated after being stirred, and the final product is obtained after complete reaction and solidification.
According to the invention, a rigid aromatic ring structure is introduced to an isocyanate molecular structure through a prepolymerization reaction to form a space network structure, a liquid B component is formed after dissolution, and after the reaction with the polyether polyol of the A component, the aromatic ring structure is connected to a polyurethane molecular structure, so that the rigidity and flame retardant property of the polyurethane elastomer are improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention selects first-order thermosetting phenolic resin with active group hydroxymethyl, in the process of heating pre-reaction with isocyanate, the hydroxymethyl reacts with isocyanate to generate carbamate group, and a space network structure is formed preliminarily and dissolved in a solvent;
(2) according to the invention, phenolic resin and isocyanate are adopted to react in advance, and a large amount of rigid aromatic rings are introduced into an isocyanate structure, so that on one hand, the advantages of excellent wear resistance, elasticity, toughness, high and adjustable curing forming speed, chemical resistance, environmental resistance and the like of thermosetting polyurethane are kept, and meanwhile, the phenolic resin has the characteristics of high rigidity, high hardness, good flame retardant property and the like, and can be widely applied to the fields of casting molds, rolling shafts, adhesives, coatings, forming materials and the like as a functional material;
(3) according to the invention, the methyl nylon carboxylate is preferably used as a solvent of the prepolymer, on one hand, the methyl nylon carboxylate has better solubility to the prepolymer compared with other organic solvents, on the other hand, the methyl nylon carboxylate is a safe and environment-friendly solvent which is non-toxic, high in flash point and easy to degrade, and the application range of the product is improved;
(4) the invention has simple and convenient operation and can carry out curing reaction at any time and any place according to field conditions.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
The safe phenolic resin modified polyurethane functional material is prepared from a component A and a component B, wherein:
TABLE 1
The preparation method comprises the following steps:
(1) replacing the prepolymerization kettle B with nitrogen for three times, adding solid phenolic resin HK-D6811, MDI-50 and nylon acid methyl ester according to the formula amount, starting stirring, heating to 60 ℃, reacting for 6 hours, and cooling to room temperature after the-NCO content in the system reaches a target value to obtain the phenolic resin and isocyanate prepolymer.
(2) Transferring the prepolymer in the step (1) into a mixing kettle B, adding PM-200 according to the formula amount, and uniformly stirring to obtain a component B;
(3) polyether polyol MN-700, DBP, TCEP, antioxidant 245, T-120 and DABCO TMR-2 are put into a mixing kettle A according to the formula amount, and the component A is obtained after uniform stirring.
(4) When in use, the A, B components are mixed according to the mass ratio of 1:1, and the mixture is poured into a mould after being uniformly stirred to be completely reacted and solidified to obtain the final product.
Example 2
The safe phenolic resin modified polyurethane functional material is prepared from a component A and a component B, wherein:
TABLE 2
The preparation method comprises the following steps:
(1) replacing the prepolymerization kettle B with nitrogen for three times, adding solid phenolic resin HK-D6811, MDI-50 and nylon acid methyl ester according to the formula amount, starting stirring, heating to 70 ℃, reacting for 4 hours, and cooling to room temperature after the-NCO content in the system reaches a target value to obtain the phenolic resin and isocyanate prepolymer.
(2) Transferring the prepolymer in the step (1) into a mixing kettle B, adding PM-200 according to the formula amount, and uniformly stirring to obtain a component B;
(3) adding polyether polyol MN-600, DINP, TCEP, antioxidant GA80, T-12 and DABCO TMR-30 into a mixing kettle A according to the formula amount, and uniformly stirring to obtain a component A.
(4) When in use, the A, B components are mixed according to the mass ratio of 1:1, and the mixture is poured into a mould after being uniformly stirred to be completely reacted and solidified to obtain the final product.
Example 3
The safe phenolic resin modified polyurethane functional material is prepared from a component A and a component B, wherein:
TABLE 3
The preparation method comprises the following steps:
(1) replacing the prepolymerization kettle B with nitrogen for three times, adding solid phenolic resin HK-D6812, MDI-50 and nylon acid methyl ester according to the formula amount, starting stirring, heating to 60 ℃, reacting for 4 hours, and cooling to room temperature after the-NCO content in the system reaches a target value to obtain the phenolic resin and isocyanate prepolymer.
(2) Transferring the prepolymer in the step (1) into a mixing kettle B, adding PM-200 according to the formula amount, and uniformly stirring to obtain a component B;
(3) adding polyether polyol MN-600, DINP, TCEP, antioxidant GA80, T-12 and DABCO TMR-30 into a mixing kettle A according to the formula amount, and uniformly stirring to obtain a component A.
(4) When in use, the A, B components are mixed according to the mass ratio of 1:1, and the mixture is poured into a mould after being uniformly stirred to be completely reacted and solidified to obtain the final product.
Comparative example 1
The component A is polyether polyol, a flame retardant, a plasticizer, an antioxidant and a catalyst, the component B is isocyanate A, isocyanate B, linear thermoplastic phenolic resin and a solvent, and the component A, B is subjected to mixing reaction according to the mass ratio of 1: 1. Wherein:
TABLE 4
The preparation method is the same as example 2.
Comparative example 2
The component A is polyether polyol, a flame retardant, a plasticizer, an antioxidant and a catalyst, the component B is isocyanate A, isocyanate B, linear thermoplastic phenolic resin and a solvent, and the component A, B is subjected to mixing reaction according to the mass ratio of 1: 1. Wherein:
TABLE 5
The preparation method is the same as example 2.
The main properties of the cured products obtained in examples 1-3 and comparative examples 1-2 were tested as shown in the following table:
TABLE 6 comparison of results
Note:
the detection basis is as follows:
GB/T2567-;
GB/T18244-2000 building waterproof material aging test method;
MT/T113-1995 coal mine underground polymer product flame-retardant antistatic property general test method and judgment rule;
GB/T2406.2-2009 plastics were tested by the oxygen index method for combustion behaviour part 2 of the room temperature test.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. A safe phenolic resin modified polyurethane functional material is characterized in that: the composite material consists of a component A and a component B, wherein the component A comprises polyether polyol, a plasticizer, a flame retardant, a catalyst and an antioxidant, and the component B comprises isocyanate A, isocyanate B, solid phenolic resin and a solvent;
the phenolic resin is first-order thermosetting phenolic resin without a curing agent, contains active group hydroxymethyl, and has a softening point of 80-100 ℃.
2. The safety type phenolic resin modified polyurethane functional material of claim 1, which is characterized in that: the polyether polyol has a functionality of 3, a hydroxyl value of 330-470 mgKOH/g, and a relative molecular weight of 350-510.
3. The safety type phenolic resin modified polyurethane functional material of claim 1, which is characterized in that: the plasticizer is one or more of dibutyl phthalate, dioctyl terephthalate or diisononyl phthalate.
4. The safety type phenolic resin modified polyurethane functional material of claim 1, which is characterized in that: the catalyst is a composite use of organic tin catalyst and trimerization catalyst.
5. The safety type phenolic resin modified polyurethane functional material of claim 4, which is characterized in that: the organotin catalyst is T-12, T-120 or T-125.
6. The safety type phenolic resin modified polyurethane functional material of claim 4, which is characterized in that: the trimerization catalyst is DABCO TMR, DABCO TMR-2, DABCO TMR-30, Polycat 41 or Polycat 46.
7. The safety type phenolic resin modified polyurethane functional material of claim 1, which is characterized in that: the antioxidant is 245, 1790 or GA 80.
8. The safety type phenolic resin modified polyurethane functional material of claim 1, which is characterized in that: the isocyanate A is polymeric MDI, the-NCO content of the isocyanate A is 30.5-32.0%, and the viscosity of the isocyanate A is 150-250 mPa & s; and the isocyanate B is MDI-50.
9. The safety type phenolic resin modified polyurethane functional material of claim 1, which is characterized in that: the solvent is one or more of N, N-dimethylformamide, nylon acid methyl ester, N-methyl pyrrolidone, tetrahydrofuran or carbon tetrachloride.
10. A method for preparing the safety type phenolic resin modified polyurethane functional material of any one of claims 1 to 9, which is characterized by comprising the following steps: the method comprises the following steps:
(1) replacing the prepolymerization kettle B with nitrogen, adding the solid phenolic resin, isocyanate B and solvent according to the formula ratio, starting stirring, heating to 60-80 ℃, reacting for 4-8 h, and cooling to room temperature after the-NCO content in the system reaches a target value to obtain a phenolic resin and isocyanate prepolymer;
(2) transferring the prepolymer in the step (1) to a mixing kettle B, adding isocyanate A according to the formula amount, and stirring to obtain a component B;
(3) putting polyether polyol, a plasticizer, a flame retardant, a catalyst and an antioxidant into a mixing kettle A according to the formula amount, and stirring to obtain a component A;
(4) when in use, the A, B components are mixed according to the calculated proportion, stirred and poured into a mould or coated, and the final product is obtained after complete reaction and solidification.
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| CN114369417A (en) * | 2021-12-29 | 2022-04-19 | 苏州世诺新材料科技有限公司 | High-speed low-peeling-force polyurethane protective film and preparation method thereof |
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| JP2005206741A (en) * | 2004-01-26 | 2005-08-04 | Dainippon Ink & Chem Inc | Resin composition for molding and molding material comprising the same |
| CN104448189A (en) * | 2014-12-03 | 2015-03-25 | 山东海冠化工科技有限公司 | Phenol-formaldehyde-resin-modified rigid polyurethane foam and preparation method thereof |
| CN109705718A (en) * | 2018-11-28 | 2019-05-03 | 耿佃勇 | Phenolic resin modified polyurethane/polyurea coating and preparation method thereof |
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| JPH07173247A (en) * | 1993-11-02 | 1995-07-11 | Nisshinbo Ind Inc | Production of polyurethane foam |
| JP2005206741A (en) * | 2004-01-26 | 2005-08-04 | Dainippon Ink & Chem Inc | Resin composition for molding and molding material comprising the same |
| CN104448189A (en) * | 2014-12-03 | 2015-03-25 | 山东海冠化工科技有限公司 | Phenol-formaldehyde-resin-modified rigid polyurethane foam and preparation method thereof |
| CN109705718A (en) * | 2018-11-28 | 2019-05-03 | 耿佃勇 | Phenolic resin modified polyurethane/polyurea coating and preparation method thereof |
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| CN114369417A (en) * | 2021-12-29 | 2022-04-19 | 苏州世诺新材料科技有限公司 | High-speed low-peeling-force polyurethane protective film and preparation method thereof |
| CN114369417B (en) * | 2021-12-29 | 2023-11-14 | 苏州世诺新材料科技有限公司 | High-speed low-peeling-force polyurethane protective film and preparation method thereof |
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