CN111995755A - Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof - Google Patents
Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof Download PDFInfo
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- CN111995755A CN111995755A CN202010856860.0A CN202010856860A CN111995755A CN 111995755 A CN111995755 A CN 111995755A CN 202010856860 A CN202010856860 A CN 202010856860A CN 111995755 A CN111995755 A CN 111995755A
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- Prior art keywords
- vinyl ester
- acid
- halogen
- unsaturated
- anhydride
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- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 74
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 57
- 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 title claims abstract description 56
- 239000003063 flame retardant Substances 0.000 title claims abstract description 56
- 229920000728 polyester Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 42
- 150000002367 halogens Chemical class 0.000 claims abstract description 42
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 40
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 33
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 17
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 16
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 17
- 150000002009 diols Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 4
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 claims description 3
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 claims description 3
- KWVKCGGJLLNVSC-UHFFFAOYSA-N 1,4-dibromo-2-ethenylbenzene Chemical compound BrC1=CC=C(Br)C(C=C)=C1 KWVKCGGJLLNVSC-UHFFFAOYSA-N 0.000 claims description 3
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 3
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 3
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYGVRVDZSPABJU-UHFFFAOYSA-N Cl[P](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound Cl[P](c1ccccc1)(c1ccccc1)c1ccccc1 WYGVRVDZSPABJU-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6828—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of a vinyl ester flame-retardant resin containing a polyester structure, which comprises the following steps: s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 130-190 ℃; s2, reacting the unsaturated polyester prepolymer with carboxyl at the two side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 105-135 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 70-80 ℃ to obtain the vinyl ester flame-retardant resin containing the polyester structure. The vinyl ester flame-retardant resin containing the polyester structure prepared by the preparation method has good fatigue resistance and flame-retardant effect.
Description
Technical Field
The invention relates to the field of vinyl ester resin, in particular to vinyl ester flame retardant resin containing a polyester structure and a preparation method thereof.
Background
The vinyl ester resin is an addition reaction product of epoxy resin and unsaturated monobasic acid containing ethylenic bonds, has unsaturated double bonds at the tail ends of resin molecular chains, is dissolved in another reactive monomer containing unsaturated double bonds, has good mechanical properties and corrosion resistance after being cured, becomes a main matrix resin of a corrosion-resistant glass fiber reinforced plastic product, is widely applied to the industries of chemical industry, petroleum, petrifaction, nonferrous metal, metallurgy, electric power, building materials and the like, and becomes a representative variety of the current corrosion-resistant resin.
However, the current vinyl ester resins and the preparation technology thereof have the following problems:
1. the carbon-carbon double bonds of the conventional vinyl ester resin are arranged at two ends of a molecular main chain, so that the crosslinking density is relatively single, the middle of the main chain is short of crosslinking points when the resin is cured, and the compactness and the fatigue resistance are common;
2. the traditional vinyl ester resin has no flame retardant effect.
Based on the situation, the invention provides a vinyl ester flame retardant resin containing a polyester structure and a preparation method thereof, which can effectively solve the problems.
Disclosure of Invention
The invention aims to provide a vinyl ester flame retardant resin containing a polyester structure and a preparation method thereof. According to the preparation method of the vinyl ester flame-retardant resin containing the polyester structure, unsaturated dicarboxylic acid (anhydride) reacts with dihydric alcohol, so that the molecular main chain of the final resin contains carbon-carbon double bonds, and the carbon-carbon double bonds of the conventional vinyl resin only exist at two ends of the molecular chain, so that the resin is in a net structure after being crosslinked and cured, and the crosslinking density and the resin activity of the resin are improved; the vinyl ester flame-retardant resin containing the polyester structure is prepared by reacting and synthesizing raw materials containing halogen, so that the molecular structure of the resin contains halogen groups to achieve a permanent flame-retardant effect, and the halogen-containing structures are quite stable at normal temperature and are decomposed at high temperature together with the surface of the resin to form HCl or HBr to inhibit flame.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a vinyl ester flame retardant resin containing a polyester structure comprises the following steps:
s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 130-190 ℃;
[ structure of which at least one contains halogen ]
S2, reacting the unsaturated polyester prepolymer with carboxyl at the two side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 105-135 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 70-80 ℃ to obtain the vinyl ester flame-retardant resin containing the polyester structure;
wherein, in step S1, at least one of the dicarboxylic acid, dicarboxylic anhydride and diol contains halogen and at least one halogen;
in step S2, the ring-opening polymerization of the epoxy group is performed, and the reaction end point is determined according to the acid value of the test reaction mixture being less than 10;
the proportion of the raw materials is calculated according to the equivalent ratio of the effective functional groups as follows: dicarboxylic acids and/or dicarboxylic anhydrides: diol ═ 2: 1.01-1.02;
[ structure of which at least one contains halogen ]
Unsaturated polyester prepolymer with carboxyl at both end groups: halogen-containing or halogen-free epoxy resin: ethylenically unsaturated monobasic acid ═ 1: 2: 1.01 to 1.03.
In the invention, the effective functional groups of dicarboxylic acid and/or dicarboxylic anhydride are carboxyl groups, wherein one anhydride is equivalent to two carboxyl groups; the effective functional group of the dihydric alcohol is hydroxyl; the effective functional group of the unsaturated polyester prepolymer of which the end groups at both sides contain carboxyl is carboxyl; the effective functional group of the halogen-containing or halogen-free epoxy resin is an epoxy group; the effective functional group of the ethylenically unsaturated monobasic acid is a carboxyl group; "and/or" refers to either one of the two or a mixture of the two, for example, dicarboxylic acid and/or dicarboxylic anhydride refers to dicarboxylic acid, dicarboxylic anhydride or a mixture of dicarboxylic acid and dicarboxylic anhydride, the same applies below.
Preferably, the dicarboxylic acid is a saturated dicarboxylic acid and/or an unsaturated dicarboxylic acid, and the dicarboxylic anhydride is a saturated dicarboxylic anhydride and/or an unsaturated dicarboxylic anhydride.
Preferably, the saturated dicarboxylic acid is any one or more of adipic acid, isophthalic acid and chlorendic acid; the saturated dicarboxylic acid anhydride is one or more of phthalic anhydride, tetrachlorophthalic anhydride, chlorendic anhydride and tetrabromophthalic anhydride.
Preferably, the unsaturated dicarboxylic acid is any one or more of chloromaleic acid, fumaric acid and maleic acid; the unsaturated dicarboxylic acid anhydride is maleic anhydride.
Preferably, the dihydric alcohol is any one or more of ethylene glycol, propylene glycol and dibromoneopentyl glycol.
Preferably, the halogen-containing or halogen-free epoxy resin is any one or more of a bromine-containing bisphenol a epoxy resin, a bromine-containing bisphenol F epoxy resin and a bisphenol F epoxy resin.
Preferably, the ethylenically unsaturated monobasic acid is any one or more of acrylic acid, methacrylic acid, crotonic acid and phenylacrylic acid.
Preferably, the reactive monomer having an unsaturated double bond is any one or more of chlorostyrene, p-chloromethylstyrene, styrene, methyl methacrylate, 2, 5-dibromostyrene, vinyltoluene and divinylbenzene.
Preferably, the catalyst is any one or more of trimethyl benzyl ammonium chloride, tetraethyl ammonium bromide, benzyl triethyl ammonium bromide, triethylamine and triphenyl phosphorus chloride; the polymerization inhibitor is any one or more of hydroquinone, methyl hydroquinone, p-benzoquinone, 2, 5-di-tert-butyl hydroquinone and tert-butyl hydroquinone.
The invention also provides a vinyl ester flame-retardant resin containing a polyester structure, and the vinyl ester flame-retardant resin containing the polyester structure is prepared by adopting the preparation method of the vinyl ester flame-retardant resin containing the polyester structure.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the preparation method of the vinyl ester flame-retardant resin containing the polyester structure, unsaturated dicarboxylic acid (anhydride) reacts with dihydric alcohol, so that the molecular main chain of the final resin contains carbon-carbon double bonds, and the carbon-carbon double bonds of the conventional vinyl resin only exist at two ends of the molecular chain, so that the resin is in a net structure after being crosslinked and cured, and the crosslinking density and the resin activity of the resin are improved; the halogen-containing structure is quite stable at normal temperature, and when exposed to flame, the halogen-containing structure and the surface of the resin are decomposed at high temperature together to form HCl or HBr, so that the flame is inhibited. The prepared vinyl ester flame-retardant resin containing the polyester structure has good fatigue resistance and flame-retardant effect.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
A preparation method of a vinyl ester flame retardant resin containing a polyester structure comprises the following steps:
s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 130-190 ℃;
[ structure of which at least one contains halogen ]
S2, reacting the unsaturated polyester prepolymer with carboxyl at the two side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 105-135 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 70-80 ℃ to obtain the vinyl ester flame-retardant resin containing the polyester structure;
wherein, in step S1, at least one of the dicarboxylic acid, dicarboxylic anhydride and diol contains halogen and at least one halogen;
in step S2, the ring-opening polymerization of the epoxy group is performed, and the reaction end point is determined according to the acid value of the test reaction mixture being less than 10;
the proportion of the raw materials is calculated according to the equivalent ratio of the effective functional groups as follows: dicarboxylic acids and/or dicarboxylic anhydrides: diol ═ 2: 1.01-1.02;
[ structure of which at least one contains halogen ]
Unsaturated polyester prepolymer with carboxyl at both end groups: halogen-containing or halogen-free epoxy resin: ethylenically unsaturated monobasic acid ═ 1: 2: 1.01 to 1.03.
In the invention, the effective functional groups of dicarboxylic acid and/or dicarboxylic anhydride are carboxyl groups, wherein one anhydride is equivalent to two carboxyl groups; the effective functional group of the dihydric alcohol is hydroxyl; the effective functional group of the unsaturated polyester prepolymer of which the end groups at both sides contain carboxyl is carboxyl; the effective functional group of the halogen-containing or halogen-free epoxy resin is an epoxy group; the effective functional group of the ethylenically unsaturated monobasic acid is a carboxyl group; "and/or" refers to either one of the two or a mixture of the two, for example, dicarboxylic acid and/or dicarboxylic anhydride refers to dicarboxylic acid, dicarboxylic anhydride or a mixture of dicarboxylic acid and dicarboxylic anhydride, the same applies below.
Preferably, the dicarboxylic acid is a saturated dicarboxylic acid and/or an unsaturated dicarboxylic acid, and the dicarboxylic anhydride is a saturated dicarboxylic anhydride and/or an unsaturated dicarboxylic anhydride.
Preferably, the saturated dicarboxylic acid is any one or more of adipic acid, isophthalic acid and chlorendic acid; the saturated dicarboxylic acid anhydride is one or more of phthalic anhydride, tetrachlorophthalic anhydride, chlorendic anhydride and tetrabromophthalic anhydride.
Preferably, the unsaturated dicarboxylic acid is any one or more of chloromaleic acid, fumaric acid and maleic acid; the unsaturated dicarboxylic acid anhydride is maleic anhydride.
Preferably, the dihydric alcohol is any one or more of ethylene glycol, propylene glycol and dibromoneopentyl glycol.
Preferably, the halogen-containing or halogen-free epoxy resin is any one or more of a bromine-containing bisphenol a epoxy resin, a bromine-containing bisphenol F epoxy resin and a bisphenol F epoxy resin.
Preferably, the ethylenically unsaturated monobasic acid is any one or more of acrylic acid, methacrylic acid, crotonic acid and phenylacrylic acid.
Preferably, the reactive monomer having an unsaturated double bond is any one or more of chlorostyrene, p-chloromethylstyrene, styrene, methyl methacrylate, 2, 5-dibromostyrene, vinyltoluene and divinylbenzene.
Preferably, the catalyst is any one or more of trimethyl benzyl ammonium chloride, tetraethyl ammonium bromide, benzyl triethyl ammonium bromide, triethylamine and triphenyl phosphorus chloride; the polymerization inhibitor is any one or more of hydroquinone, methyl hydroquinone, p-benzoquinone, 2, 5-di-tert-butyl hydroquinone and tert-butyl hydroquinone.
The invention also provides a vinyl ester flame-retardant resin containing a polyester structure, and the vinyl ester flame-retardant resin containing the polyester structure is prepared by adopting the preparation method of the vinyl ester flame-retardant resin containing the polyester structure.
Example 1:
a preparation method of a vinyl ester flame retardant resin containing a polyester structure comprises the following steps:
s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 130 ℃;
s2, reacting the unsaturated polyester prepolymer with carboxyl at both side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 105 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 70 ℃ to obtain the vinyl ester flame-retardant resin containing the polyester structure;
wherein, in step S1, at least one of the dicarboxylic acid, dicarboxylic anhydride and diol contains halogen and at least one halogen;
in step S2, the ring-opening polymerization of the epoxy group is performed, and the reaction end point is determined according to the acid value of the test reaction mixture being less than 10;
the proportion of the raw materials is calculated according to the equivalent ratio of the effective functional groups as follows: dicarboxylic acids and/or dicarboxylic anhydrides: diol ═ 2: 1.01;
unsaturated polyester prepolymer with carboxyl at both end groups: halogen-containing or halogen-free epoxy resin: ethylenically unsaturated monobasic acid ═ 1: 2: 1.01.
example 2:
a preparation method of a vinyl ester flame retardant resin containing a polyester structure comprises the following steps:
s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 190 ℃;
s2, reacting the unsaturated polyester prepolymer with carboxyl at both side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 135 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 80 ℃ to obtain the vinyl ester flame-retardant resin containing the polyester structure;
wherein, in step S1, at least one of the dicarboxylic acid, dicarboxylic anhydride and diol contains halogen and at least one halogen;
in step S2, the ring-opening polymerization of the epoxy group is performed, and the reaction end point is determined according to the acid value of the test reaction mixture being less than 10;
the proportion of the raw materials is calculated according to the equivalent ratio of the effective functional groups as follows: dicarboxylic acids and/or dicarboxylic anhydrides: diol ═ 2: 1.02;
unsaturated polyester prepolymer with carboxyl at both end groups: halogen-containing or halogen-free epoxy resin: ethylenically unsaturated monobasic acid ═ 1: 2: 1.03.
example 3:
a preparation method of a vinyl ester flame retardant resin containing a polyester structure comprises the following steps:
s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 148 ℃;
s2, reacting the unsaturated polyester prepolymer with carboxyl at both side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 120 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 74 ℃ to obtain the vinyl ester flame-retardant resin containing the polyester structure;
wherein, in step S1, at least one of the dicarboxylic acid, dicarboxylic anhydride and diol contains halogen and at least one halogen;
in step S2, the ring-opening polymerization of the epoxy group is performed, and the reaction end point is determined according to the acid value of the test reaction mixture being less than 10;
the proportion of the raw materials is calculated according to the equivalent ratio of the effective functional groups as follows: dicarboxylic acids and/or dicarboxylic anhydrides: diol ═ 2: 1.014;
unsaturated polyester prepolymer with carboxyl at both end groups: halogen-containing or halogen-free epoxy resin: ethylenically unsaturated monobasic acid ═ 1: 2: 1.018.
example 4:
a preparation method of a vinyl ester flame retardant resin containing a polyester structure comprises the following steps:
s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 164 ℃;
s2, reacting the unsaturated polyester prepolymer with carboxyl at both side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 125 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 77 ℃ to obtain the vinyl ester flame-retardant resin containing a polyester structure;
wherein, in step S1, at least one of the dicarboxylic acid, dicarboxylic anhydride and diol contains halogen and at least one halogen;
in step S2, the ring-opening polymerization of the epoxy group is performed, and the reaction end point is determined according to the acid value of the test reaction mixture being less than 10;
the proportion of the raw materials is calculated according to the equivalent ratio of the effective functional groups as follows: dicarboxylic acids and/or dicarboxylic anhydrides: diol ═ 2: 1.017;
unsaturated polyester prepolymer with carboxyl at both end groups: halogen-containing or halogen-free epoxy resin: ethylenically unsaturated monobasic acid ═ 1: 2: 1.024.
the raw materials in examples 1 to 4 of the present invention are specifically shown in table 1 below:
TABLE 1
Note: when a plurality of components (substances) are involved in each raw material in the above table 1, the mass of each component (substance) is equal; for example, dicarboxylic acids: the mass of the isophthalic acid and the fumaric acid are equal.
The vinyl ester flame retardant resins containing polyester structures obtained in examples 1 to 4 of the present invention were subjected to performance tests, and the test results are shown in table 2:
TABLE 2
As can be seen from the above table, the vinyl ester flame retardant resin containing polyester structure of the present invention has the following advantages:
good fatigue resistance and good flame retardant property.
From the analysis of the above table, it can be seen that the flame retardant effect of the conventional vinyl ester resin is general, the flame retardant property of the product of the invention is good, the flame retardant property can reach the effect of self-extinguishing plastic or even flame-retardant plastic according to the oxygen index, the flame retardant effect is better after some flame retardant is added, and the effect of the flame retardant property grade B1 (flame-retardant material) can be reached.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. The preparation method of the vinyl ester flame retardant resin containing the polyester structure is characterized by comprising the following steps:
s1, carrying out polycondensation reaction on dicarboxylic acid and/or dicarboxylic anhydride and dihydric alcohol to obtain an unsaturated polyester prepolymer of which the end groups on both sides contain carboxyl; controlling the reaction temperature of the polycondensation reaction to be 130-190 ℃;
s2, reacting the unsaturated polyester prepolymer with carboxyl at the two side end groups obtained in the step S1 with halogen-containing or halogen-free epoxy resin and ethylenic bond-containing unsaturated monoacid in the presence of a catalyst and a polymerization inhibitor to perform ring-opening polymerization of epoxy groups, wherein the reaction temperature is 105-135 ℃, and reacting to form vinyl ester resin; then dissolving the mixture in a reactive monomer containing unsaturated double bonds, and controlling the temperature at 70-80 ℃ to obtain the vinyl ester flame-retardant resin containing the polyester structure;
wherein, in step S1, at least one of the dicarboxylic acid, dicarboxylic anhydride and diol contains halogen and at least one halogen;
in step S2, the ring-opening polymerization of the epoxy group is performed, and the reaction end point is determined according to the acid value of the test reaction mixture being less than 10;
the proportion of the raw materials is calculated according to the equivalent ratio of the effective functional groups as follows: dicarboxylic acids and/or dicarboxylic anhydrides: diol ═ 2: 1.01-1.02;
unsaturated polyester prepolymer with carboxyl at both end groups: halogen-containing or halogen-free epoxy resin: ethylenically unsaturated monobasic acid ═ 1: 2: 1.01 to 1.03.
2. The method of claim 1, wherein the dicarboxylic acid is a saturated dicarboxylic acid and/or an unsaturated dicarboxylic acid, and the dicarboxylic acid anhydride is a saturated dicarboxylic acid anhydride and/or an unsaturated dicarboxylic acid anhydride.
3. The method for preparing vinyl ester flame retardant resin containing polyester structure as claimed in claim 1, wherein said saturated dicarboxylic acid is any one or more of adipic acid, isophthalic acid and chlorendic acid; the saturated dicarboxylic acid anhydride is one or more of phthalic anhydride, tetrachlorophthalic anhydride, chlorendic anhydride and tetrabromophthalic anhydride.
4. The method for preparing vinyl ester flame retardant resin containing polyester structure as claimed in claim 2, wherein said unsaturated dicarboxylic acid is any one or more of chloromaleic acid, fumaric acid and maleic acid; the unsaturated dicarboxylic acid anhydride is maleic anhydride.
5. The method for preparing vinyl ester flame retardant resin containing polyester structure according to claim 1, wherein the diol is any one or more of ethylene glycol, propylene glycol and dibromoneopentyl glycol.
6. The method of claim 1, wherein the halogen-containing or halogen-free epoxy resin is any one or more of a bromine-containing bisphenol a epoxy resin, a bromine-containing bisphenol F epoxy resin, and a bisphenol F epoxy resin.
7. The method for preparing the vinyl ester flame retardant resin containing the polyester structure according to claim 1, wherein the ethylenically unsaturated monoacid is any one or more of acrylic acid, methacrylic acid, crotonic acid and phenylacrylic acid.
8. The method for preparing vinyl ester flame retardant resin containing polyester structure as claimed in claim 1, wherein the reactive monomer containing unsaturated double bond is any one or more of chlorostyrene, p-chloromethylstyrene, styrene, methyl methacrylate, 2, 5-dibromostyrene, vinyl toluene and divinyl benzene.
9. The method for preparing vinyl ester flame retardant resin containing polyester structure as claimed in claim 1, wherein the catalyst is any one or more of trimethyl benzyl ammonium chloride, tetraethyl ammonium bromide, benzyl triethyl ammonium bromide, triethylamine and triphenyl phosphonium chloride; the polymerization inhibitor is any one or more of hydroquinone, methyl hydroquinone, p-benzoquinone, 2, 5-di-tert-butyl hydroquinone and tert-butyl hydroquinone.
10. A flame retardant vinyl ester resin containing a polyester structure, wherein the flame retardant vinyl ester resin containing a polyester structure is prepared by the method for preparing the flame retardant vinyl ester resin containing a polyester structure according to any one of claims 1 to 9.
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