CN113754835A - Grease-based modified unsaturated polyester resin and preparation method thereof - Google Patents
Grease-based modified unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN113754835A CN113754835A CN202110920824.0A CN202110920824A CN113754835A CN 113754835 A CN113754835 A CN 113754835A CN 202110920824 A CN202110920824 A CN 202110920824A CN 113754835 A CN113754835 A CN 113754835A
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- unsaturated polyester
- acid
- based modified
- modified unsaturated
- grease
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 88
- 239000004519 grease Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 99
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 59
- 239000000194 fatty acid Substances 0.000 claims abstract description 59
- 229930195729 fatty acid Natural products 0.000 claims abstract description 59
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 59
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims abstract description 58
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims abstract description 58
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 39
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000728 polyester Polymers 0.000 claims abstract description 38
- 239000000539 dimer Substances 0.000 claims abstract description 36
- -1 amino compound Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 80
- 239000000376 reactant Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 52
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005086 pumping Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 description 49
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 48
- 239000003921 oil Substances 0.000 description 37
- 235000019198 oils Nutrition 0.000 description 37
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 34
- 239000003795 chemical substances by application Substances 0.000 description 30
- 229960004063 propylene glycol Drugs 0.000 description 28
- 229920006395 saturated elastomer Polymers 0.000 description 23
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 235000013772 propylene glycol Nutrition 0.000 description 8
- 238000010125 resin casting Methods 0.000 description 8
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 8
- FQYHHEJETOLDHR-UHFFFAOYSA-K butyl(chloro)tin(2+);dihydroxide Chemical compound CCCC[Sn](O)(O)Cl FQYHHEJETOLDHR-UHFFFAOYSA-K 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 5
- CUXYLFPMQMFGPL-WPOADVJFSA-N (9Z,11E,13E)-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C/CCCCCCCC(O)=O CUXYLFPMQMFGPL-WPOADVJFSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical group CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
Abstract
The embodiment of the specification provides an oil-based modified unsaturated polyester resin and a preparation method thereof. Specifically, the preparation method comprises the following steps: (1) carrying out polycondensation reaction on isophthalic acid and dihydric alcohol under the action of a catalyst to obtain a polyester prepolymer; (2) mixing the polyester prepolymer prepared in the step (1) with maleic anhydride, dihydric alcohol, an amino compound, dimeric fatty acid and eleostearic acid, and heating to react to obtain grease-based modified unsaturated polyester; (3) and (3) uniformly mixing the grease-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the grease-based modified unsaturated polyester resin. According to the technical scheme provided by the specification, flexible monomer dimer fatty acid and eleostearic acid with different proportions are added into unsaturated polyester by an in-situ polymerization method, and the flexibility of the unsaturated polyester resin is improved by utilizing the in-situ toughening and synergistic effects of the dimer fatty acid and the eleostearic acid on molecular chain segments of the unsaturated polyester resin.
Description
Technical Field
The embodiment of the specification relates to the technical field of materials, in particular to an oil-based modified unsaturated polyester resin and a preparation method thereof.
Background
Unsaturated Polyester Resin (UPR) is a kind of multifunctional thermosetting resin synthesized by melting and polycondensing Unsaturated polybasic acid (anhydride), saturated polybasic acid (anhydride) and saturated polyalcohol, dissolving them in cross-linking monomer containing vinyl group and solidifying. The composite material is formed under normal pressure, has flexible technological performance, excellent mechanical performance, heat resistance and corrosion resistance, and is widely applied to the fields of navigation, building materials, chemical industry, automobiles and the like. However, unsaturated polyester resins have a highly cross-linked and rigid benzene ring structure between molecules after curing, which results in low toughness, poor crack propagation resistance and poor impact strength of the materials, and limits the application of the materials in production practice.
Disclosure of Invention
In view of the above, an object of the present disclosure is to provide a method for preparing an oil-based modified unsaturated polyester resin, so as to overcome the defects in the prior art. Another object of the present specification is to provide an oil-and-fat-based modified unsaturated polyester resin.
In view of the above objects, in a first aspect, the present specification provides a method for preparing an oil-and-fat-based modified unsaturated polyester resin, including:
(1) carrying out polycondensation reaction on isophthalic acid and dihydric alcohol under the action of a catalyst to obtain a polyester prepolymer;
(2) mixing the polyester prepolymer prepared in the step (1) with maleic anhydride, dihydric alcohol, an amino compound, dimeric fatty acid and eleostearic acid, and heating to react to obtain grease-based modified unsaturated polyester;
(3) and (3) uniformly mixing the grease-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the grease-based modified unsaturated polyester resin.
Further, the step (1) specifically includes:
uniformly mixing isophthalic acid, dihydric alcohol and a catalyst, and reacting at 155-170 ℃ for 0.5-1.5 hours under the protection of nitrogen;
and heating to 190-205 ℃ for continuous reaction until the acid value is reduced to below 20mg KOH/g, thus obtaining the polyester prepolymer.
Further, the step (2) specifically includes:
uniformly mixing the polyester prepolymer with maleic anhydride, dihydric alcohol, an amino compound, dimeric fatty acid and eleostearic acid, and reacting at 150-170 ℃ for 0.5-1.5 hours;
and then heating to 195-205 ℃, and carrying out vacuum pumping reaction for 3-5 hours to obtain the grease-based modified unsaturated polyester.
Further, the step (2) is preceded by:
cooling the polyester prepolymer prepared in the step (1) to 130-140 ℃.
Further, the amino compound is selected from one or more of ethylenediamine and hexamethylenediamine.
Further, the molar percentage of the amino compound in the reactant is 0-1.5%; wherein the reactants comprise isophthalic acid, glycol, maleic anhydride, an amino compound, a dimerized fatty acid, and eleostearic acid.
Further, the crosslinking agent is selected from at least two of styrene, acrylic acid, vinyl toluene, hydroxyethyl methacrylate and methacrylic acid.
Further, the cross-linking agent accounts for 25-40% of the total mass of the grease-based modified unsaturated polyester resin.
Further, the mole percentage content of the dimer fatty acid in the reactant is 1-8%; and/or
The molar percentage content of the eleostearic acid in the reactant is 1-8%; wherein the reactants comprise isophthalic acid, glycol, maleic anhydride, an amino compound, a dimerized fatty acid, and eleostearic acid.
In a second aspect, the present specification also provides an oil-and-fat-based modified unsaturated polyester resin obtained by any one of the above-described production methods.
As can be seen from the above description, in the preparation method of the grease-based modified unsaturated polyester resin provided in one or more embodiments of the present specification, the flexible monomeric dimeric fatty acid and the elaeostearic acid with different ratios are added into the unsaturated polyester by the in-situ polymerization method, and the dimeric fatty acid and the elaeostearic acid are utilized to toughen the molecular chain segment of the unsaturated polyester resin in situ, so as to improve the flexibility of the unsaturated polyester resin. Based on amidation reaction, the unsaturated polyester structure is modified, and the hydrogen bond function in the polyester chain segment is enhanced, so that a tighter cross-linked network structure is formed in the unsaturated polyester resin, and the problem of serious strength reduction caused by only using grease-based modified resin is solved.
Drawings
In order to more clearly illustrate one or more embodiments or prior art solutions of the present specification, the drawings that are needed in the description of the embodiments or prior art will be briefly described below, and it is obvious that the drawings in the following description are only one or more embodiments of the present specification, and that other drawings may be obtained by those skilled in the art without inventive effort from these drawings.
Fig. 1 is a schematic flow chart of a method for preparing an oil-and-fat-based modified unsaturated polyester resin according to one or more embodiments of the present disclosure;
fig. 2 is another schematic flow chart of a preparation method of the grease-based modified unsaturated polyester resin according to one or more embodiments of the present disclosure.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
It is to be noted that unless otherwise defined, technical or scientific terms used in one or more embodiments of the present specification should have the ordinary meaning as understood by those of ordinary skill in the art to which this disclosure belongs. The use of "first," "second," and similar terms in one or more embodiments of the specification is not intended to indicate any order, quantity, or importance, but rather is used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items.
Because of resource crisis and environmental issues associated with fossil-based traditional polymers, sustainable polymers derived from renewable feedstocks are attracting increasing attention. In recent years, with the continuous increase of global oil productivity, the breakthrough of processes such as ultrasonic enhanced extraction and molecular distillation in oil purification application promotes the rapid development of oil and its processing industry, and provides sufficient raw materials for resource utilization of vegetable oil and its derivatives.
In view of the above, in a first aspect of the embodiments of the present specification, there is provided a preparation method for improving the performance of an unsaturated polyester resin by using a unique long methylene chain and a single ring structure in a dimerized fatty acid, eleostearic acid, so as to solve the technical defects of low toughness, poor crack propagation resistance and poor impact strength of the unsaturated polyester resin in the prior art.
Specifically, referring to fig. 1, the preparation method of the grease-based modified unsaturated polyester resin includes:
(1): m-phthalic acid and dihydric alcohol are subjected to polycondensation reaction under the action of a catalyst to obtain the polyester prepolymer.
Alternatively, the molar ratio of isophthalic acid to glycol is 1: (1.3-1.7). Wherein the dihydric alcohol is selected from one or more of 1, 2-propylene glycol and ethylene glycol.
Illustratively, the molar ratio of isophthalic acid to glycol is 1:1.3, 1:1.4, 1:1.5, 1:1.55, 1:1.6, or 1: 1.7.
Optionally, the catalyst is selected from one or more of p-toluenesulfonic acid, stannous chloride, monobutyl tin oxide, monobutyl dihydroxytin chloride.
Optionally, the mass percentage of the catalyst in the reactant in the step (1) is 0.3-2.2%. The reactants of step (1) include isophthalic acid, glycol, and the catalyst.
Illustratively, the mass percentage may be 0.3%, 0.5%, 0.6%, 0.8%, 1.1%, 1.3%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, or 2.2%.
(2): and (2) mixing the polyester prepolymer prepared in the step (1) with maleic anhydride, dihydric alcohol, an amino compound, dimeric fatty acid and eleostearic acid, and heating to react to obtain the grease-based modified unsaturated polyester.
In this step, the diol is one or more selected from 1, 2-propanediol and ethylene glycol. It should be understood that the diols in this step and the diol in step (1) are independently selected, i.e., the diols in the two steps may be the same or different.
Optionally, the molar ratio of the acids to the diols in the preparation of the grease-based modified unsaturated polyester is: acids: 1-diol: (1.0-1.5). Illustratively, the molar ratio of acid to glycol can be 1:1.0, 1:1.2, 1:1.3, 1:1.4, or 1: 1.5.
Wherein the acids include saturated acids and unsaturated acids. Wherein the saturated acid comprises isophthalic acid; the unsaturated acids include dimer fatty acids, eleostearic acid, and maleic anhydride.
Optionally, the molar ratio of saturated to unsaturated acids is: saturated acid: (0.4-1.2) of an unsaturated acid. Exemplary, saturated acids: unsaturated acids ═ 1:0.4, 1:0.6, 1:0.8, 1:0.9, 1:1.0, or 1: 1.2.
In the research process, the inventor of the application finds that when only dimerized fatty acid and eleostearic acid are added into a polyester prepolymer, the strength of the obtained modified unsaturated polyester is seriously reduced, and the application requirement is difficult to meet. Therefore, the inventors tried to add other components for improving the strength of the unsaturated polyester, and found that the amino compound is effective in improving the technical problem of strength reduction caused by the simple use of the grease-based modified unsaturated polyester. Specifically, based on amidation reaction, an amino compound is utilized to modify the structure of the oil-based modified unsaturated polyester, and the hydrogen bond effect in the polyester chain segment is enhanced, so that a tighter cross-linked network structure is formed in the resin, and the technical effect of improving the strength of the oil-based modified unsaturated polyester is achieved.
As an alternative embodiment, the amino compound is selected from one or more of ethylenediamine, hexamethylenediamine. The ethylene diamine and the hexamethylene diamine contain two amino groups and have short carbon chains, can effectively improve polyester chains and form a cross-linked network structure, and have the advantages of high reaction efficiency and stable structure.
Optionally, the molar percentage of the amino compound in the reactant is 0-1.5%; wherein the reactants comprise isophthalic acid, glycol, maleic anhydride, an amino compound, a dimerized fatty acid, and eleostearic acid.
Illustratively, the mole percentage may be 0.1%, 0.5%, 0.8%, 0.9%, 1.1%, 1.2%, 1.4%, 1.5%, 1.7%, 1.8%, 1.9%, 2.0%, 2.3%, or 2.5%.
Due to the content limitation, the amino compound can be ensured to effectively improve the structure of the oil-based modified unsaturated polyester, and the effect of improving the strength is achieved.
(3): and (3) uniformly mixing the grease-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the grease-based modified unsaturated polyester resin.
Optionally, the polymerization inhibitor is selected from one or more of hydroquinone and methyl hydroquinone.
The content of the polymerization inhibitor is not particularly limited. Optionally, the mass of the polymerization inhibitor is 0.03 to 0.07 percent, such as 0.03, 0.04, 0.05 or 0.07 percent of the mass of the grease-based modified unsaturated polyester resin obtained in the step (3).
Optionally, the cross-linking agent is selected from at least two of styrene, acrylic acid, vinyl toluene, hydroxyethyl methacrylate, methacrylic acid. Compared with the prior art, the method has the advantages that the content of styrene in the resin is reduced by limiting the type of the cross-linking agent, so that the toxicity of the grease-based modified unsaturated polyester resin can be effectively reduced.
Optionally, the cross-linking agent accounts for 25-40% of the total mass of the grease-based modified unsaturated polyester resin, such as 25%, 30%, 32%, 35%, 38% or 40%. By limiting the addition amount of the cross-linking agent, the grease-based modified unsaturated polyester obtained in the step (2) and the cross-linking agent can be fully cross-linked, and simultaneously, the introduction of a large amount of styrene can be avoided.
As can be seen from the above description, in the preparation method of the grease-based modified unsaturated polyester resin provided in one or more embodiments of the present specification, the in-situ polymerization method is adopted to add the flexible monomeric dimeric fatty acid and the elaeostearic acid in different proportions into the unsaturated polyester, and the dimeric fatty acid and the elaeostearic acid are utilized to toughen the molecular chain segments of the unsaturated polyester resin in situ, so as to improve the flexibility of the unsaturated polyester resin. Based on amidation reaction, the unsaturated polyester structure is modified, and the hydrogen bond function in the polyester chain segment is enhanced, so that a tighter cross-linked network structure is formed in the unsaturated polyester resin, and the problem of serious strength reduction caused by only using grease-based modified resin is solved.
In one or more embodiments of the present disclosure, a curing step is also included. Specifically, the curing step comprises:
and (3) uniformly mixing the grease-based modified unsaturated polyester resin obtained in the step (3) with an accelerator and a curing agent, placing the mixture in a preset mold, curing for 2-4 hours at 60 ℃, and curing for 1-2 hours at 110 ℃.
Optionally, the promoter is cobalt naphthenate. Further, the addition amount of the accelerator is 1 to 2% by mass, for example, 1.1%, 1.3%, 1.6%, 1.9% by mass of the grease-based modified unsaturated polyester resin obtained in the step (3).
Optionally, the curing agent is methyl ethyl ketone peroxide. Further, the addition amount of the curing agent is 0.5 to 1.5% by mass, for example, 0.6%, 0.8%, 1.1%, 1.3% by mass of the grease-based modified unsaturated polyester resin obtained in the step (3).
For a curing time at 60 ℃, it may be 2 hours, 2.3 hours, 2.5 hours, 3.0 hours, 3.3 hours, or 4 hours.
For curing at 110 ℃ it may be 1 hour, 1.2 hours, 1.5 hours, 1.6 hours, 1.8 hours or 2 hours.
It should be noted that other accelerators and curing agents can be selected by those skilled in the art according to the needs, and are not listed here.
To facilitate removal of the cured resin from the pre-set mold, in some embodiments, a release agent is coated within the pre-set mold. The kind of the release agent is not limited.
In one or more embodiments of the present disclosure, a more detailed method for preparing the grease-based modified unsaturated polyester resin is also provided. Specifically, referring to fig. 2, the step (1) specifically includes:
uniformly mixing isophthalic acid, dihydric alcohol and a catalyst, and reacting at 155-170 ℃ for 0.5-1.5 hours under the protection of nitrogen; illustratively, the reaction is carried out under nitrogen at 155 ℃ for 1.5 hours, at 160 ℃ for 1.1 hours, at 165 ℃ for 1.0 hour, or at 170 ℃ for 0.5 hour.
And heating to 190-205 ℃, and continuing to react until the acid value is reduced to below 20mg KOH/g, thus obtaining the polyester prepolymer. The reaction time is usually 3 to 4 hours. Illustratively, the temperature is raised to 190 ℃ for 4 hours, 195 ℃ for 3.8 hours, 200 ℃ for 3.5 hours, or 205 ℃ for 3 hours.
Optionally, the temperature is increased to 190-205 ℃ and the reaction is continued for 3-4 hours under the protection of nitrogen.
In some embodiments, the step (2) specifically includes:
uniformly mixing the polyester prepolymer with maleic anhydride, dihydric alcohol, an amino compound, dimeric fatty acid and eleostearic acid, and reacting at 150-170 ℃ for 0.5-1.5 hours; illustratively, the reaction is carried out at 150 ℃ for 1.4 hours, 153 ℃ for 1.3 hours, 165 ℃ for 1.0 hour, or 170 ℃ for 0.6 hour.
Heating to 195-205 ℃, and carrying out vacuum pumping reaction for 3-5 hours to obtain the grease-based modified unsaturated polyester; illustratively, the reaction is carried out at 195 ℃ for 4.5 hours, 198 ℃ for 4.0 hours, 200 ℃ for 3.5 hours, or 205 ℃ for 3.0 hours.
The reactor for producing the fat-based modified unsaturated polyester is equipped with a stirrer, a thermometer, an air inlet, a reflux pipe, and the like.
Here, the mixing of the reactants in each step can be achieved by providing a stirrer. The thermometer enables temperature control of the reaction process. The air inlet and the return pipe can ensure the realization of nitrogen atmosphere and vacuum environment.
In some embodiments, the step (2) is preceded by: cooling the polyester prepolymer prepared in the step (1) to 130-140 ℃, such as 132 ℃, 135 ℃ or 138 ℃.
As an alternative embodiment, the dimer fatty acid may be present in the reactants in a molar percentage of 1 to 8%, for example 2%, 2.8%, 3.5%, 4.1%, 4.9%, 5.3%, 6.1%, 7.3% or 7.8%; wherein the reactants comprise isophthalic acid, glycol, maleic anhydride, an amino compound, a dimerized fatty acid, and eleostearic acid.
As an alternative embodiment, the molar percentage of the eleostearic acid in the reactant is 1 to 8%, such as 1.7%, 2.4%, 3.3%, 4.2%, 4.7%, 5.3%, 6.2%, 7.1% or 7.9%; wherein the reactants comprise isophthalic acid, glycol, maleic anhydride, an amino compound, a dimerized fatty acid, and eleostearic acid.
The molar percentage contents of the dimerized fatty acid and the eleostearic acid in reactants are respectively limited, so that the strength and the flexibility of the grease-based modified unsaturated polyester are balanced, and the influence of the grease-based modified unsaturated polyester on the strength is reduced while the flexibility of the grease-based modified unsaturated polyester is improved.
In a second aspect of the embodiments of the present specification, there is also provided an oil-and-fat-based modified unsaturated polyester resin obtained by any one of the above-described production methods. The grease-based modified unsaturated polyester resin of the above embodiment is obtained by the corresponding preparation method in any one of the foregoing embodiments, and has the beneficial effects of the corresponding method embodiment, which are not described herein again.
In order to further explain the present invention, the following detailed description will be made on the method for producing an oil-and-fat-based modified unsaturated polyester resin according to the present invention, with reference to examples and comparative examples. The reagents used in the following examples are all commercially available.
Example 1
The embodiment provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propanediol and monobutyltin oxide in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 163 ℃, reacting for 1 hour under the protection of nitrogen, and then heating to 203 ℃ again to react for 3.7 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.4 percent; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, hexamethylene diamine, dimer fatty acid and eleostearic acid, heating to 160 ℃, reacting for 1.5 hours, then heating to 200 ℃, and performing vacuum pumping reaction for 3.2 hours to obtain the grease-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28mg KOH/g.
Wherein, the molar ratio of acids to 1, 2-propylene glycol is 1:1.23 based on all reactants in the step (1) and the step (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.85; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the mole percentage of the hexamethylene diamine is 0.5% based on the total reactants of the step (1) and the step (2).
Wherein the mole percentage of the dimer fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of the eleostearic acid is 1.0 percent based on all reactants in the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding an accelerator and a curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 3 hours and 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Wherein the cross-linking agent is methyl styrene and acrylic acid, and the molar ratio of the acrylic acid to the methyl styrene is 1: 1; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Example 2
The embodiment provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propanediol and monobutyltin oxide in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 160 ℃, reacting for 1.2 hours under the protection of nitrogen, and then heating to 203 ℃ again to react for 3.5 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.5 percent; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, hexamethylene diamine, dimer fatty acid and eleostearic acid, heating to 160 ℃, reacting for 1.5 hours, then heating to 203 ℃, and performing vacuum pumping reaction for 3.5 hours to obtain the grease-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28 mgKOH/g.
Wherein, the molar ratio of acids to 1, 2-propylene glycol is 1:1.25 based on all reactants in the step (1) and the step (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.86; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of the hexamethylene diamine is 1.0% based on the total reactants in the steps (1) and (2).
Wherein the mole percentage of the dimer fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of the eleostearic acid is 1.0 percent based on all reactants in the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding the accelerator and the curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 3.5 hours and at 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Wherein the cross-linking agent is styrene and acrylic acid, and the molar ratio of the acrylic acid to the styrene is 1: 1; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Example 3
The embodiment provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propanediol and monobutyltin oxide in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 165 ℃, reacting for 1 hour under the protection of nitrogen, and then heating to 205 ℃ again to react for 3.5 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.4 percent; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, hexamethylene diamine, dimer fatty acid and eleostearic acid, heating to 160 ℃, reacting for 1 hour, then heating to 203 ℃, and performing vacuum pumping reaction for 3.5 hours to obtain the grease-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28 mgKOH/g.
Wherein, the molar ratio of acids to 1, 2-propylene glycol is 1:1.23 based on all reactants in the step (1) and the step (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.84; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of the hexamethylene diamine is 1.5% based on the total reactants of the step (1) and the step (2).
Wherein the mole percentage of the dimer fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of the eleostearic acid is 1.0 percent based on all reactants in the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding an accelerator and a curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 3 hours and 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
The crosslinking agent is styrene and methacrylic acid, and the molar ratio of the methacrylic acid to the styrene is 1: 1; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Example 4
The embodiment provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propanediol and a catalyst in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 165 ℃, reacting for 1 hour under the protection of nitrogen, and then heating to 205 ℃ again to react for 3.5 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the catalyst is monobutyl dihydroxy tin chloride and monobutyl tin oxide, the mass percentage of the monobutyl dihydroxy tin chloride in the reactant is 0.4%, and the mass percentage of the monobutyl tin oxide in the reactant is 0.2%; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, ethylene glycol, ethylenediamine, dimer fatty acid and eleostearic acid, heating to 165 ℃ for reaction for 1 hour, then heating to 203 ℃ again, and carrying out vacuum pumping reaction for 3 hours to obtain the oil-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28mg KOH/g.
Wherein, the molar ratio of acids to alcohols is 1:1.23 based on all reactants in the steps (1) and (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.87; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of the ethylenediamine based on the total reactants in the steps (1) and (2) is 0.5%.
Wherein the mole percentage of the dimerized fatty acid is 3.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of the eleostearic acid is 1.5 percent based on all reactants in the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding an accelerator and a curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 3 hours and 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Wherein the cross-linking agent is styrene and acrylic acid, and the molar ratio of the acrylic acid to the styrene is 1: 2; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Example 5
The embodiment provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propanediol and monobutyl dihydroxy tin chloride in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 165 ℃, reacting for 1 hour under the protection of nitrogen, and then heating to 205 ℃ again to react for 3.5 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the mass percentage of the monobutyl dihydroxy tin chloride in the reactant is 0.6 percent; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, ethylene glycol, ethylenediamine, dimer fatty acid and eleostearic acid, heating to 165 ℃ for reaction for 1.5 hours, then heating to 203 ℃ again, and carrying out vacuum pumping reaction for 4 hours to obtain the oil-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28 mgKOH/g.
Wherein, the molar ratio of acids to alcohols is 1:1.23 based on all reactants in the steps (1) and (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.86; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of the ethylenediamine based on the total reactants in the steps (1) and (2) is 1.0%.
Wherein the mole percentage of the dimer fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of the eleostearic acid is 1.0 percent based on all reactants in the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding the accelerator and the curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 2.5 hours and at 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
The crosslinking agent is styrene and methacrylic acid, and the molar ratio of the methacrylic acid to the styrene is 1: 1; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Example 6
The embodiment provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propanediol and monobutyl dihydroxy tin chloride in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 165 ℃, reacting for 1 hour under the protection of nitrogen, and then heating to 205 ℃ again to react for 3.5 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the mass percentage of the monobutyl dihydroxy tin chloride in the reactant is 0.6 percent; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, ethylenediamine, dimer fatty acid and eleostearic acid, heating to 155 ℃, reacting for 1 hour, then heating to 203 ℃, and performing vacuum pumping reaction for 3 hours to obtain the oil-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28 mgKOH/g.
Wherein, the molar ratio of acids to 1, 2-propylene glycol is 1:1.23 based on all reactants in the step (1) and the step (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.85; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of the ethylenediamine based on the total reactants in the steps (1) and (2) is 1.5%.
Wherein the mole percentage of the dimer fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of the eleostearic acid is 1.0 percent based on all reactants in the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding an accelerator and a curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 3 hours and 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
The crosslinking agent is styrene and methacrylic acid, and the molar ratio of the methacrylic acid to the styrene is 1: 1; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Example 7
The embodiment provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propylene glycol and stannous chloride in a reaction vessel provided with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 160 ℃, reacting for 1 hour under the protection of nitrogen, and then heating to 195 ℃ again to react for 3 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the mass percentage of the stannous chloride in the reactant is 0.5 percent; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, ethylene glycol, ethylenediamine, dimer fatty acid and eleostearic acid, heating to 155 ℃, reacting for 1 hour, then heating to 203 ℃, and performing vacuum pumping reaction for 3 hours to obtain the oil-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28mg KOH/g.
Wherein, the molar ratio of acids to alcohols is 1:1.23 based on all reactants in the steps (1) and (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.85; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of the ethylenediamine based on the total reactants in the steps (1) and (2) is 2.0%.
Wherein the mole percentage of the dimerized fatty acid is 2% based on the total reactants of step (1) and step (2).
Wherein the eleostearic acid accounts for 4 mol percent based on all reactants in the steps (1) and (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding an accelerator and a curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 3 hours and 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Wherein the cross-linking agent is styrene and hydroxyethyl methacrylate, and the molar ratio of the hydroxyethyl methacrylate to the styrene is 2: 1; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Comparative example 1
The comparative example provides a preparation method of an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) placing isophthalic acid, 1, 2-propanediol and monobutyltin oxide in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a reflux pipe; heating the mixture to 160 ℃, reacting for 1 hour under the protection of nitrogen, and then heating to 201 ℃ again to react for 3.5 hours to obtain a polyester prepolymer; wherein the mol ratio of the isophthalic acid to the 1, 2-propylene glycol is 1: 1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.4 percent; the reaction end point is that the acid value in the step (1) is reduced to be below 20mg KOH/g.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, dimer fatty acid and eleostearic acid, heating to 160 ℃, reacting for 1.5 hours, then heating to 200 ℃, and vacuumizing and reacting for 3 hours to obtain the grease-based modified unsaturated polyester; wherein, the reaction end point is that the acid value in the step (2) is reduced to be below 28 mgKOH/g.
Wherein, the molar ratio of acids to 1, 2-propylene glycol is 1:1.23 based on all reactants in the step (1) and the step (2), and the acids comprise isophthalic acid, maleic anhydride, dimer fatty acid and eleostearic acid. Further, the molar ratio of saturated acids to unsaturated acids is 1: 0.42; wherein the saturated acid comprises isophthalic acid; the unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the mole percentage of the dimer fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of the eleostearic acid is 1.0 percent based on all reactants in the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, sequentially adding hydroquinone and a cross-linking agent into a reaction vessel, and uniformly stirring to obtain the oil-based modified unsaturated polyester resin; the resin casting was prepared as follows: sequentially adding an accelerator and a curing agent into a resin system, uniformly stirring, pouring into a mold coated with a release agent, and curing at 60 ℃ for 3 hours and 110 ℃ for 1.5 hours.
Wherein the addition amount of the hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Wherein the cross-linking agent is styrene and acrylic acid, and the molar ratio of the acrylic acid to the styrene is 1: 1; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
Wherein the addition amount of the accelerator and the curing agent is 1 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Comparative example 2
The comparative example differs from example 5 in that only eleostearic acid is added, and the molar percentage of eleostearic acid is 5.5%.
Comparative example 3 this comparative example differs from example 5 in that the crosslinking agent is styrene; the cross-linking agent accounts for 33 percent of the total mass of the grease-based modified unsaturated polyester resin.
The resin molded bodies obtained in examples 1 to 7 and comparative examples 1 to 3 were subjected to mechanical property tests. Specifically, mechanical properties were tested on a commercial tensile tester, model CMT 6503. The test method refers to the methods GB/T1040-1992 and GB/T9341-2000, and the test results are shown in Table 1.
TABLE 1 comparison of mechanical Properties of resin cast bodies (25 ℃ C.)
From the above results, it can be seen that the grease-based modified unsaturated polyester resins obtained in examples 1 to 7 have excellent tensile strength, elastic modulus, bending strength and elongation at break, and can meet the application requirements of materials in transportation and electronic parts. Examples 1-3 are the oil-based modification and the hexamethylenediamine modification of unsaturated polyester resin, wherein example 2 has the best mechanical properties, the tensile strength and the elastic modulus reach 22.2MPa and 535.4MPa, and the elongation at break also reaches 41.6%, so that the application requirements are met. Examples 4 to 7 are to carry out grease-based modification and ethylenediamine modification on unsaturated polyester resin, and example 5 has the best mechanical properties, the tensile strength and the elastic modulus reach 23.1MPa and 505.0MPa, and the elongation at break also reaches 38.5%, so that the application requirements are met.
Comparative example 1 does not carry out modification treatment of amine compounds, comparative example 2 only adopts eleostearic acid for modification of resin, and comparative example 3 only adopts styrene as a reactive diluent, so that mechanical properties of the obtained product are reduced to different degrees.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the spirit of the present disclosure, features from the above embodiments or from different embodiments may also be combined, steps may be implemented in any order, and there are many other variations of different aspects of one or more embodiments of the present description as described above, which are not provided in detail for the sake of brevity.
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (10)
1. A preparation method of an oil-based modified unsaturated polyester resin is characterized by comprising the following steps:
(1) carrying out polycondensation reaction on isophthalic acid and dihydric alcohol under the action of a catalyst to obtain a polyester prepolymer;
(2) mixing the polyester prepolymer prepared in the step (1) with maleic anhydride, dihydric alcohol, an amino compound, dimeric fatty acid and eleostearic acid, and heating to react to obtain grease-based modified unsaturated polyester;
(3) and (3) uniformly mixing the grease-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the grease-based modified unsaturated polyester resin.
2. The preparation method according to claim 1, wherein the step (1) specifically comprises:
uniformly mixing isophthalic acid, dihydric alcohol and a catalyst, and reacting at 155-170 ℃ for 0.5-1.5 hours under the protection of nitrogen;
and heating to 190-205 ℃ for continuous reaction until the acid value is reduced to below 20mg KOH/g, thus obtaining the polyester prepolymer.
3. The preparation method according to claim 1, wherein the step (2) specifically comprises:
uniformly mixing the polyester prepolymer with maleic anhydride, dihydric alcohol, an amino compound, dimeric fatty acid and eleostearic acid, and reacting at 150-170 ℃ for 0.5-1.5 hours;
and then heating to 195-205 ℃, and carrying out vacuum pumping reaction for 3-5 hours to obtain the grease-based modified unsaturated polyester.
4. The method of claim 3, wherein the step (2) is preceded by:
cooling the polyester prepolymer prepared in the step (1) to 130-140 ℃.
5. The method according to claim 1, wherein the amino compound is one or more selected from the group consisting of ethylenediamine and hexamethylenediamine.
6. The preparation method according to claim 1, wherein the molar percentage of the amino compound in the reactant is 0-1.5%; wherein the reactants comprise isophthalic acid, glycol, maleic anhydride, an amino compound, a dimerized fatty acid, and eleostearic acid.
7. The method according to claim 1, wherein the crosslinking agent is at least two selected from the group consisting of styrene, acrylic acid, vinyl toluene, methacrylic acid, and hydroxyethyl methacrylate.
8. The method according to claim 1, wherein the crosslinking agent accounts for 25 to 40% of the total mass of the grease-based modified unsaturated polyester resin.
9. The method of claim 1, wherein the dimer fatty acid is present in the reactant in a molar percentage of 1 to 8%; and/or
The molar percentage content of the eleostearic acid in the reactant is 1-8%; wherein the reactants comprise isophthalic acid, glycol, maleic anhydride, an amino compound, a dimerized fatty acid, and eleostearic acid.
10. The oil-and-fat-based modified unsaturated polyester resin obtained by the production method according to any one of claims 1 to 9.
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