CN113754835B - Grease-based modified unsaturated polyester resin and preparation method thereof - Google Patents
Grease-based modified unsaturated polyester resin and preparation method thereof Download PDFInfo
- Publication number
- CN113754835B CN113754835B CN202110920824.0A CN202110920824A CN113754835B CN 113754835 B CN113754835 B CN 113754835B CN 202110920824 A CN202110920824 A CN 202110920824A CN 113754835 B CN113754835 B CN 113754835B
- Authority
- CN
- China
- Prior art keywords
- acid
- unsaturated polyester
- based modified
- modified unsaturated
- polyester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 89
- 239000004519 grease Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 100
- 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 62
- 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 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 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
- 239000000539 dimer Substances 0.000 claims abstract description 47
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 44
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- -1 amino compound Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 80
- 239000000376 reactant Substances 0.000 claims description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 35
- 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 20
- 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 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 46
- 239000003921 oil Substances 0.000 description 40
- 235000019198 oils Nutrition 0.000 description 40
- 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
- 150000007513 acids Chemical class 0.000 description 29
- 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
- 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 11
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 10
- 235000013772 propylene glycol Nutrition 0.000 description 10
- 238000010125 resin casting Methods 0.000 description 10
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 9
- 238000003756 stirring Methods 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 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
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 238000000465 moulding 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
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 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
- 230000035484 reaction time Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
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) Performing 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, amino compound, dimer fatty acid and eleostearic acid, and heating for reaction to obtain grease-based modified unsaturated polyester; (3) And (3) uniformly mixing the oil-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the oil-based modified unsaturated polyester resin. According to the technical scheme provided by the specification, the in-situ polymerization method is adopted to add the flexible monomer dimer fatty acid and eleostearic acid with different proportions into the unsaturated polyester, and the molecular chain segments of the unsaturated polyester resin are toughened in situ by utilizing the dimer fatty acid and eleostearic acid, so that the flexibility of the unsaturated polyester resin is improved.
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 resins (Unsaturated polyester resin, UPR) are multifunctional thermosetting resins which are prepared by melt polycondensation of unsaturated polybasic acid (anhydride), saturated polybasic acid (anhydride) and saturated polyol, and then dissolution of the resultant resin in vinyl-containing crosslinking monomers, and solidification of the resultant resin. The molding process has flexible technological performance, excellent mechanical performance, heat resistance and corrosion resistance, and may be used widely in navigation, building material, chemical industry, automobile and other fields. However, the unsaturated polyester resin has a highly crosslinked and rigid benzene ring structure among molecules after being cured, so that the toughness of the material is low, the crack extension resistance and the impact strength are poor, and the application of the unsaturated polyester resin in production practice is limited.
Disclosure of Invention
In view of the above, it is an object of the present specification to provide a process for producing an oil-based modified unsaturated polyester resin, which overcomes the drawbacks of the prior art. It is another object of the present specification to provide a grease-based modified unsaturated polyester resin.
In view of the above object, in a first aspect, embodiments of the present specification provide a method for preparing an oil-based modified unsaturated polyester resin, comprising:
(1) Performing 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, amino compound, dimer fatty acid and eleostearic acid, and heating for reaction to obtain grease-based modified unsaturated polyester;
(3) And (3) uniformly mixing the oil-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the oil-based modified unsaturated polyester resin.
Further, the step (1) specifically includes:
uniformly mixing isophthalic acid, dihydric alcohol and a catalyst, and reacting for 0.5-1.5 hours at 155-170 ℃ under the protection of nitrogen;
and heating to 190-205 ℃ to continue the 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, amino compound, dimer fatty acid and eleostearic acid, and reacting for 0.5-1.5 hours at 150-170 ℃;
then heating to 195-205 ℃, and vacuumizing to react for 3-5 hours to obtain the grease-based modified unsaturated polyester.
Further, before the step (2), the method further comprises:
and (3) 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 mole percentage content of the amino compound in the reactant is 0 to 1.5 percent; wherein the reactants include isophthalic acid, glycol, maleic anhydride, amino compounds, dimer fatty acids, and eleostearic acid.
Further, the cross-linking agent is at least two selected from 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 mole percentage content of eleostearic acid in the reactant is 1-8%; wherein the reactants include isophthalic acid, glycol, maleic anhydride, amino compounds, dimer fatty acids, and eleostearic acid.
In a second aspect, the present description examples also provide a grease-based modified unsaturated polyester resin obtained by any of the foregoing preparation methods.
From the above, it can be seen that the preparation method of the grease-based modified unsaturated polyester resin provided in one or more embodiments of the present disclosure adopts an in-situ polymerization method to add flexible monomer dimer fatty acid and eleostearic acid with different proportions into the unsaturated polyester, and uses the dimer fatty acid and eleostearic acid to toughen the molecular chain segments of the unsaturated polyester resin in situ, thereby improving the flexibility of the unsaturated polyester resin. Based on amidation reaction, the unsaturated polyester structure is modified to strengthen the hydrogen bond action in the polyester chain segment, so that a tighter cross-linked network structure is formed inside the unsaturated polyester resin, and the problem of serious strength reduction caused by using only the grease-based modified resin is solved.
Drawings
For a clearer description of one or more embodiments of the present description or of the solutions of the prior art, the drawings that are necessary for the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only one or more embodiments of the present description, from which other drawings can be obtained, without inventive effort, for a person skilled in the art.
FIG. 1 is a schematic flow diagram of a method of preparing a grease-based modified unsaturated polyester resin according to one or more embodiments of the present disclosure;
FIG. 2 is a schematic flow diagram of another method for preparing a grease-based modified unsaturated polyester resin according to one or more embodiments of the present disclosure.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same.
It is noted that unless otherwise defined, technical or scientific terms used in one or more embodiments of the present disclosure should be taken in a general sense as understood by one of ordinary skill in the art to which the present disclosure pertains. The use of the terms "first," "second," and the like in one or more embodiments of the present description does not denote any order, quantity, or importance, but rather the terms "first," "second," and the like are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof, but does not exclude other elements or items.
Sustainable polymers derived from renewable raw materials have attracted increasing attention due to resource crisis and environmental concerns associated with fossil-based traditional polymers. In recent years, with the continuous increase of global grease productivity, the breakthroughs of ultrasonic enhanced extraction, molecular distillation and other processes in grease purification application promote the rapid development of grease and processing industry thereof, and provide sufficient raw materials for the resource utilization of vegetable oil and derivatives thereof.
Based on this, in the first aspect of the embodiments of the present specification, 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 dimer fatty acid and eleostearic acid is provided, so as to solve the technical defects of low toughness, poor crack extension 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): and (3) carrying out polycondensation reaction on isophthalic acid and dihydric alcohol under the action of a catalyst to obtain the polyester prepolymer.
Optionally, 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 and monobutyl dihydroxy tin chloride.
Optionally, the mass percentage of the catalyst in the reactant in the step (1) is 0.3-2.2%. The reactant in the step (1) comprises isophthalic acid, dihydric alcohol and the catalyst.
Illustratively, the mass percent 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 (3) mixing the polyester prepolymer prepared in the step (1) with maleic anhydride, dihydric alcohol, amino compound, dimerized fatty acid and eleostearic acid, and heating for reaction to obtain the grease-based modified unsaturated polyester.
The dihydric alcohol in the step is one or more selected from 1, 2-propylene glycol and ethylene glycol. It should be understood that the diol in this step and the diol in step (1) are each independently selected, i.e., the diols in the two steps may be the same or different.
Optionally, the mole ratio of the acid to the dihydric alcohol in the preparation of the grease-based modified unsaturated polyester is as follows: acids: diol=1: (1.0-1.5). Illustratively, the molar ratio of acid to glycol may be 1:1.0, 1:1.2, 1:1.3, 1:1.4, or 1:1.5.
Wherein the acids include saturated 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 acid to unsaturated acid is: saturated acid: unsaturated acid=1, (0.4 to 1.2). Exemplary, saturated acids: unsaturated acid=1:0.4, 1:0.6, 1:0.8, 1:0.9, 1:1.0 or 1:1.2.
The inventors of the present application found that when only dimer fatty acid and eleostearic acid were added to the polyester prepolymer during the course of the study, the strength of the resulting modified unsaturated polyester was severely reduced, and it was difficult to satisfy the demands of the application. For this reason, the inventors have tried to add other components for improving the strength of unsaturated polyesters, and found that amino compounds can effectively solve the technical problem that the mere use of an oil-based modified unsaturated polyester leads to a decrease in strength. Specifically, based on amidation reaction, amino compound is utilized to modify the oil-based modified unsaturated polyester structure, and the hydrogen bond action 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 and hexamethylenediamine. The ethylenediamine and the hexamethylenediamine contain two amino groups and have shorter carbon chains, so that the polyester chain can be effectively improved, a crosslinked network structure can be formed, and the method has the advantages of high reaction efficiency and stable structure.
Optionally, the amino compound accounts for 0 to 1.5 percent of the mole of the reactant; wherein the reactants include isophthalic acid, glycol, maleic anhydride, amino compounds, dimer fatty acids, and eleostearic acid.
Illustratively, the mole percent 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%.
The content limitation can ensure that the amino compound effectively improves the structure of the grease-based modified unsaturated polyester, thereby achieving the effect of improving the strength.
(3): and (3) uniformly mixing the oil-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the oil-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. Alternatively, the polymerization inhibitor is 0.03 to 0.07%, for example 0.03%, 0.04%, 0.05% or 0.07% of the mass of the grease-based modified unsaturated polyester resin obtained in step (3).
Optionally, the cross-linking agent is selected from at least two of styrene, acrylic acid, vinyl toluene, hydroxyethyl methacrylate, methacrylic acid. By limiting the kind of the crosslinking agent, the content of styrene in the resin is reduced compared with the prior art, so that the toxicity of the grease-based modified unsaturated polyester resin can be effectively reduced.
Optionally, the cross-linking agent comprises 25 to 40%, such as 25%, 30%, 32%, 35%, 38% or 40% of the total mass of the grease-based modified unsaturated polyester resin. By limiting the amount of the crosslinking agent added, the grease-based modified unsaturated polyester obtained in the step (2) and the crosslinking agent can be ensured to be sufficiently crosslinked, and simultaneously, the introduction of a large amount of styrene can be avoided.
From the above, the preparation method of the grease-based modified unsaturated polyester resin provided by one or more embodiments of the present disclosure adopts an in-situ polymerization method to add flexible monomer dimer fatty acid and eleostearic acid with different proportions into unsaturated polyester, and uses the dimer fatty acid and eleostearic acid to toughen the molecular chain segments of the unsaturated polyester resin in situ, thereby improving the flexibility of the unsaturated polyester resin in a synergistic effect. Based on amidation reaction, the unsaturated polyester structure is modified to strengthen the hydrogen bond action in the polyester chain segment, so that a tighter cross-linked network structure is formed inside the unsaturated polyester resin, and the problem of serious strength reduction caused by using only the 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 includes:
uniformly mixing the oil-based modified unsaturated polyester resin obtained in the step (3), an accelerator and a curing agent, placing the mixture in a preset mold, curing the mixture for 2 to 4 hours at 60 ℃ and curing the mixture for 1 to 2 hours at 110 ℃.
Optionally, the promoter is cobalt naphthenate. Further, the accelerator is added in an amount of 1 to 2% by mass, for example, 1.1%, 1.3%, 1.6% and 1.9% by mass, based on the mass of the oil-based modified unsaturated polyester resin obtained in the step (3).
Optionally, the curing agent is methyl ethyl ketone peroxide. Further, the amount of the curing agent added is 0.5 to 1.5% by mass, for example, 0.6%, 0.8%, 1.1% by mass, 1.3% by mass, based on the mass of the oil-based modified unsaturated polyester resin obtained in the step (3).
For curing times 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, those skilled in the art may select other accelerators and curing agents as required, which are not exemplified herein.
To facilitate removal of the cured resin from the pre-set mold, in some embodiments, the pre-set mold is coated with a release agent. The kind of the release agent is not limited.
In one or more embodiments of the present specification, a more detailed method of 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 for 0.5-1.5 hours at 155-170 ℃ under the protection of nitrogen; exemplary, the reaction is carried out at 155℃for 1.5 hours, 160℃for 1.1 hour, 165℃for 1.0 hour, or 170℃for 0.5 hour under nitrogen protection.
Heating to 190-205 ℃ and continuing to react until the acid value is reduced to below 20mg KOH/g, thus obtaining the polyester prepolymer. Typically, the reaction time is 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 raised to 190-205 ℃ to continue the reaction for 3-4 hours, and the reaction is also under the protection of nitrogen.
In some embodiments, the step (2) specifically includes:
uniformly mixing the polyester prepolymer with maleic anhydride, dihydric alcohol, amino compound, dimer fatty acid and eleostearic acid, and reacting for 0.5-1.5 hours at 150-170 ℃; exemplary, at 150 ℃ for 1.4 hours, 153 ℃ for 1.3 hours, 165 ℃ for 1.0 hour, or 170 ℃ for 0.6 hours.
Then heating to 195-205 ℃, and vacuumizing to react for 3-5 hours to obtain the grease-based modified unsaturated polyester; exemplary, 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 oil-based modified unsaturated polyester is provided with a stirrer, a thermometer, an air inlet, a return pipe, and the like.
Here, the provision of the stirrer enables uniform mixing of the reactants in each step. The thermometer can realize temperature control on the reaction process. The realization of nitrogen atmosphere and vacuum environment can be guaranteed to air inlet and back flow.
In some embodiments, the step (2) further comprises, prior to: cooling the polyester prepolymer produced in step (1) to 130-140 ℃, e.g. 132 ℃, 135 ℃ or 138 ℃.
As an alternative embodiment, the dimer fatty acid is present in the reactant in a mole percent of 1 to 8%, such as 2%, 2.8%, 3.5%, 4.1%, 4.9%, 5.3%, 6.1%, 7.3% or 7.8%; wherein the reactants include isophthalic acid, glycol, maleic anhydride, amino compounds, dimer fatty acids, and eleostearic acid.
As an alternative embodiment, the mole percentage of eleostearic acid in the reactants is 1-8%, for example 1.7%, 2.4%, 3.3%, 4.2%, 4.7%, 5.3%, 6.2%, 7.1% or 7.9%; wherein the reactants include isophthalic acid, glycol, maleic anhydride, amino compounds, dimer fatty acids, and eleostearic acid.
The molar percentage contents of the dimer fatty acid and the eleostearic acid in the reactant are respectively limited, so that the strength and the flexibility of the grease-based modified unsaturated polyester are balanced, and the influence on the strength of the grease-based modified unsaturated polyester is reduced while the flexibility of the grease-based modified unsaturated polyester is improved.
In a second aspect of the embodiments herein, there is also provided a grease-based modified unsaturated polyester resin obtained by any of the preparation methods described above. The grease-based modified unsaturated polyester resin of the above embodiment is obtained according to the corresponding preparation method of any of the foregoing embodiments, and has the beneficial effects of the corresponding method embodiments, which are not described herein.
In order to further illustrate the present invention, the following is a detailed description of the preparation method of the oil-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 monobutyl tin oxide in a reaction vessel equipped with a mechanical stirrer, thermometer, air inlet and return tube; the mixture is heated to 163 ℃ and reacted for 1 hour under the protection of nitrogen, and then the temperature is again heated to 203 ℃ and reacted for 3.7 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.4 percent; the acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, hexamethylenediamine, dimerized fatty acid and eleostearic acid, heating to 160 ℃ for reaction for 1.5 hours, then heating to 200 ℃ again, and vacuumizing for reaction for 3.2 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to below 28mg KOH/g to be the reaction end point.
Wherein the molar ratio of acids to 1, 2-propanediol is 1:1.23 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.85; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of hexamethylenediamine is 0.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of dimerized fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 1.0 percent based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 3 hours at 60 ℃ and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of 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% 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% 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 monobutyl tin oxide in a reaction vessel equipped with a mechanical stirrer, thermometer, air inlet and return tube; the mixture is heated to 160 ℃ and reacts for 1.2 hours under the protection of nitrogen, and then is heated to 203 ℃ again for 3.5 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.5 percent; the acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, hexamethylenediamine, dimerized fatty acid and eleostearic acid, heating to 160 ℃ for reaction for 1.5 hours, then heating to 203 ℃ again, and vacuumizing for reaction for 3.5 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to 28mgKOH/g or less as the reaction end point.
Wherein the molar ratio of acids to 1, 2-propanediol is 1:1.25 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.86; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of hexamethylenediamine is 1.0% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of dimerized fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 1.0 percent based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 3.5 hours at 60 ℃, and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of 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% 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% 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 monobutyl tin oxide in a reaction vessel equipped with a mechanical stirrer, thermometer, air inlet and return tube; the mixture is heated to 165 ℃ and reacts for 1 hour under the protection of nitrogen, and then is heated to 205 ℃ again for 3.5 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.4 percent; the acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(2) Cooling the polyester prepolymer obtained in the step (1) to 140 ℃, adding maleic anhydride, 1, 2-propylene glycol, hexamethylenediamine, dimerized fatty acid and eleostearic acid, heating to 160 ℃ for reaction for 1 hour, then heating to 203 ℃ again, and vacuumizing for reaction for 3.5 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to 28mgKOH/g or less as the reaction end point.
Wherein the molar ratio of acids to 1, 2-propanediol is 1:1.23 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.84; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of hexamethylenediamine is 1.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of dimerized fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 1.0 percent based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 3 hours at 60 ℃ and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of 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 methacrylic acid, and the molar ratio of the methacrylic acid to the styrene is 1:1; the cross-linking agent accounts for 33% 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% 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 return tube; the mixture is heated to 165 ℃ and reacts for 1 hour under the protection of nitrogen, and then is heated to 205 ℃ again for 3.5 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the catalyst is monobutyl dihydroxy tin chloride and monobutyl tin oxide, wherein 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 acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(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 vacuumizing for reaction for 3 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to below 28mg KOH/g to be the reaction end point.
Wherein the molar ratio of acids to alcohols is 1:1.23 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.87; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of ethylenediamine is 0.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of dimerized fatty acid is 3.5% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 1.5% based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 3 hours at 60 ℃ and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of 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% 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% 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-propylene glycol and monobutyl dihydroxy tin chloride in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a return pipe; the mixture is heated to 165 ℃ and reacts for 1 hour under the protection of nitrogen, and then is heated to 205 ℃ again for 3.5 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the mass percentage of the monobutyl dihydroxy tin chloride in the reactant is 0.6%; the acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(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, and then heating to 203 ℃ again for vacuuming reaction for 4 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to 28mgKOH/g or less as the reaction end point.
Wherein the molar ratio of acids to alcohols is 1:1.23 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.86; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage content of the ethylenediamine is 1.0 percent based on the total reactants of the step (1) and the step (2).
Wherein the molar percentage of dimerized fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 1.0 percent based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 2.5 hours at 60 ℃, and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of 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 methacrylic acid, and the molar ratio of the methacrylic acid to the styrene is 1:1; the cross-linking agent accounts for 33% 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% 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-propylene glycol and monobutyl dihydroxy tin chloride in a reaction vessel equipped with a mechanical stirrer, a thermometer, an air inlet and a return pipe; the mixture is heated to 165 ℃ and reacts for 1 hour under the protection of nitrogen, and then is heated to 205 ℃ again for 3.5 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the mass percentage of the monobutyl dihydroxy tin chloride in the reactant is 0.6%; the acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(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 ℃ for reaction for 1 hour, then heating to 203 ℃ again, and vacuumizing for reaction for 3 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to 28mgKOH/g or less as the reaction end point.
Wherein the molar ratio of acids to 1, 2-propanediol is 1:1.23 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.85; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of ethylenediamine is 1.5% based on the total reactants of step (1) and step (2).
Wherein the molar percentage of dimerized fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 1.0 percent based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 3 hours at 60 ℃ and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of 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 methacrylic acid, and the molar ratio of the methacrylic acid to the styrene is 1:1; the cross-linking agent accounts for 33% 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% 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 return pipe; the mixture is heated to 160 ℃ and reacts for 1 hour under the protection of nitrogen, and then is heated to 195 ℃ again to react for 3 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the mass percentage of stannous chloride in the reactant is 0.5%; the acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(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 ℃ for reaction for 1 hour, then heating to 203 ℃ again, and vacuumizing for reaction for 3 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to below 28mg KOH/g to be the reaction end point.
Wherein the molar ratio of acids to alcohols is 1:1.23 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.85; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage content of the ethylenediamine is 2.0 percent based on the total reactants of the step (1) and the step (2).
Wherein the molar percentage of the dimerized fatty acid is 2% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 4% based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 3 hours at 60 ℃ and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of hydroquinone is 0.05 percent of the mass of the obtained grease-based modified unsaturated polyester resin.
Wherein the cross-linking agent is styrene or hydroxyethyl methacrylate, and the molar ratio of the hydroxyethyl methacrylate to the styrene is 2:1; the cross-linking agent accounts for 33% 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% of the mass of the obtained grease-based modified unsaturated polyester resin.
Comparative example 1
The comparative example provides a method for preparing an oil-based modified unsaturated polyester resin, which comprises the following steps:
(1) Placing isophthalic acid, 1, 2-propanediol and monobutyl tin oxide in a reaction vessel equipped with a mechanical stirrer, thermometer, air inlet and return tube; the mixture is heated to 160 ℃ and reacts for 1 hour under the protection of nitrogen, and then is heated to 201 ℃ again for 3.5 hours to prepare polyester prepolymer; wherein, the molar ratio of isophthalic acid to 1, 2-propylene glycol is 1:1.375; the mass percentage of the monobutyl tin oxide in the reactant is 0.4 percent; the acid value in the step (1) is reduced to below 20mg KOH/g to be the reaction end point.
(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 ℃ for reaction for 1.5 hours, then heating to 200 ℃ again, and vacuumizing for reaction for 3 hours to obtain the grease-based modified unsaturated polyester; wherein the acid value in the step (2) is reduced to 28mgKOH/g or less as the reaction end point.
Wherein the molar ratio of acids to 1, 2-propanediol is 1:1.23 based on the total reactants of step (1) and step (2), said acids including isophthalic acid, maleic anhydride, dimer fatty acid, and eleostearic acid. Further, the molar ratio of saturated acid to unsaturated acid is 1:0.42; wherein the saturated acid comprises isophthalic acid; unsaturated acids include maleic anhydride, dimer fatty acids, and eleostearic acid.
Wherein the molar percentage of dimerized fatty acid is 4.5% based on the total reactants of step (1) and step (2).
Wherein the mole percentage of eleostearic acid is 1.0 percent based on the total reactants of the step (1) and the step (2).
(3) After the oil-based modified unsaturated polyester obtained in the step (2) is cooled, hydroquinone and a cross-linking agent are sequentially added into a reaction container, and uniformly stirred, so that the oil-based modified unsaturated polyester resin is obtained; the preparation of the resin casting body comprises the following steps: sequentially adding the accelerator and the curing agent into the resin system, uniformly stirring, pouring into a mold coated with the release agent, curing for 3 hours at 60 ℃ and curing for 1.5 hours at 110 ℃.
Wherein, the addition amount of 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% 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% of the mass of the obtained grease-based modified unsaturated polyester resin.
Comparative example 2
The difference between this comparative example and example 5 is that only eleostearic acid was added and the mole percent of eleostearic acid was 5.5%.
Comparative example 3 this comparative example differs from example 5 in that the cross-linking agent is styrene; the cross-linking agent accounts for 33% of the total mass of the grease-based modified unsaturated polyester resin.
The resin casting materials obtained in examples 1 to 7 and comparative examples 1 to 3 were subjected to mechanical properties. Specifically, the mechanical property test was performed on a commercial tensile tester of the CMT6503 type. Test methods refer to GB/T1040-1992 and GB/T9341-2000 methods, and the test results are shown in Table 1.
TABLE 1 comparison of mechanical Properties of resin castings (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 the materials in transportation and electronic parts. Examples 1 to 3 were oil-based and hexamethylenediamine-modified unsaturated polyester resins, wherein the mechanical properties of example 2 were optimal, the tensile strength and elastic modulus reached 22.2MPa and 535.4MPa, and the elongation at break reached 41.6%, meeting the application requirements. Examples 4 to 7 were obtained by modifying an unsaturated polyester resin with a grease base and an ethylenediamine, and example 5 was found to have the best mechanical properties, and the tensile strength and elastic modulus were 23.1MPa and 505.0MPa, and the elongation at break was 38.5%, which were satisfactory for applications.
Comparative example 1 was not subjected to amine compound modification treatment, comparative example 2 was modified with eleostearic acid only for the resin, and comparative example 3 was modified with styrene only as a reactive diluent, and the mechanical properties of the obtained product were reduced to various degrees.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the disclosure, including the claims, is limited to these examples; combinations of features of the above embodiments or in different embodiments are also possible within the spirit of the present disclosure, steps may be implemented in any order, and there are many other variations of the different aspects of one or more embodiments described above which are not provided in detail for the sake of brevity.
The present disclosure is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments of the disclosure, are therefore intended to be included within the scope of the disclosure.
Claims (7)
1. The preparation method of the grease-based modified unsaturated polyester resin is characterized by comprising the following steps:
(1) Performing 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, amino compound, dimer fatty acid and eleostearic acid, and heating for reaction to obtain grease-based modified unsaturated polyester;
(3) Uniformly mixing the oil-based modified unsaturated polyester obtained in the step (2) with a polymerization inhibitor and a cross-linking agent to obtain the oil-based modified unsaturated polyester resin; wherein,
the step (1) specifically comprises the following steps:
uniformly mixing isophthalic acid, dihydric alcohol and a catalyst, and reacting for 0.5-1.5 hours at 155-170 ℃ under the protection of nitrogen;
heating to 190-205 ℃ to continue the reaction until the acid value is reduced to below 20mg KOH/g, thus obtaining the polyester prepolymer; the step (2) specifically comprises:
uniformly mixing the polyester prepolymer with maleic anhydride, dihydric alcohol, amino compound, dimer fatty acid and eleostearic acid, and reacting at 150-170 ℃ for 0.5-1.5 hours;
then heating to 195-205 ℃, and vacuumizing for 3-5 hours to obtain the grease-based modified unsaturated polyester;
wherein the cross-linking agent is selected from one of four combinations of methyl styrene and acrylic acid, styrene and methacrylic acid, styrene and hydroxyethyl methacrylate.
2. The method of claim 1, wherein the step (2) is preceded by the further steps of:
and (3) cooling the polyester prepolymer prepared in the step (1) to 130-140 ℃.
3. The method according to claim 1, wherein the amino compound is one or more selected from ethylenediamine and hexamethylenediamine.
4. The preparation method of claim 1, wherein the amino compound is 0-1.5% by mole in the reactant; wherein the reactants include isophthalic acid, glycol, maleic anhydride, amino compounds, dimer fatty acids, and eleostearic acid.
5. The preparation method of claim 1, wherein the cross-linking agent accounts for 25-40% of the total mass of the oil-based modified unsaturated polyester resin.
6. The preparation method of claim 1, wherein the molar percentage of the dimer fatty acid in the reactant is 1-8%; and/or
The mole percentage content of eleostearic acid in the reactant is 1-8%; wherein the reactants include isophthalic acid, glycol, maleic anhydride, amino compounds, dimer fatty acids, and eleostearic acid.
7. The oil-based modified unsaturated polyester resin obtained by the preparation method according to any one of claims 1 to 6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110920824.0A CN113754835B (en) | 2021-08-11 | 2021-08-11 | Grease-based modified unsaturated polyester resin and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110920824.0A CN113754835B (en) | 2021-08-11 | 2021-08-11 | Grease-based modified unsaturated polyester resin and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113754835A CN113754835A (en) | 2021-12-07 |
CN113754835B true CN113754835B (en) | 2024-03-12 |
Family
ID=78788990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110920824.0A Active CN113754835B (en) | 2021-08-11 | 2021-08-11 | Grease-based modified unsaturated polyester resin and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113754835B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PT117321A (en) * | 2021-07-01 | 2023-01-02 | Inst Superior Tecnico | HIGH PERFORMANCE UNSATURATED POLYESTER RESINS BASED ON RENEWABLE RESOURCES |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB942646A (en) * | 1961-07-25 | 1963-11-27 | Us Rubber Co | Polyester resin compositions |
US4343743A (en) * | 1979-12-10 | 1982-08-10 | Rhone-Poulenc Industries | Novel polyesteramides having low glass transition temperatures |
JPS6424304A (en) * | 1987-07-20 | 1989-01-26 | Toshiba Chem Corp | Resin composition material for processing transformer |
JPH02194018A (en) * | 1989-01-20 | 1990-07-31 | Kuraray Co Ltd | Polyester and resin composition for coating material |
WO2008067967A2 (en) * | 2006-12-08 | 2008-06-12 | Uniqema B.V. | Unsaturated polymers |
CN101802046A (en) * | 2007-07-12 | 2010-08-11 | 陶氏环球技术公司 | Room temperature curable polymers and precursors thereof |
CN102875785A (en) * | 2011-07-13 | 2013-01-16 | 比亚迪股份有限公司 | Polyamide modified polyester resin and preparation method thereof, and automotive primer surfacer containing polyester resin |
CN104497286A (en) * | 2014-01-26 | 2015-04-08 | 南京长江涂料有限公司 | Renewable alkyd resin with high solid portion and preparation method of enamel paint |
CN104725624A (en) * | 2013-12-23 | 2015-06-24 | 常州华科聚合物股份有限公司 | Unsaturated polyester resin for metal plate putty, and preparation method thereof |
CN106674504A (en) * | 2016-12-23 | 2017-05-17 | 仲恺农业工程学院 | Method for synthesizing unsaturated polyester by using C36 dimer fatty acid |
CN107602829A (en) * | 2017-09-19 | 2018-01-19 | 株洲时代新材料科技股份有限公司 | A kind of flexible unsaturated polyester resin and its preparation method and application |
CN107936185A (en) * | 2017-12-15 | 2018-04-20 | 仲恺农业工程学院 | A kind of modified unsaturated polyester resin and preparation method thereof |
CN111196873A (en) * | 2018-11-20 | 2020-05-26 | 万华化学集团股份有限公司 | Alkyd resin, double-crosslinked alkyd acrylate dispersion comprising alkyd resin, preparation method and application |
CN111205446A (en) * | 2020-02-28 | 2020-05-29 | 衡阳山泰化工有限公司 | High-temperature-resistant organic amine modified polyester resin and preparation method and application thereof |
CN111848935A (en) * | 2020-08-11 | 2020-10-30 | 广州德恒致远科技有限公司 | Amide group-containing biodegradable copolyester and preparation method thereof |
CN112646155A (en) * | 2020-12-21 | 2021-04-13 | 浙江光华科技股份有限公司 | Amide-modified polyester resin for powder coating and powder coating |
CN112979933A (en) * | 2021-04-07 | 2021-06-18 | 安庆瑞泰化工有限公司 | Biomass polyacid modified polyester resin and preparation method thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX2011001814A (en) * | 2008-08-18 | 2011-09-01 | Cook Composites & Polymers | Resin and paint coating compositions comprising highly esterified polyol polyesters with one pair of conjugated double bonds. |
GB201418762D0 (en) * | 2014-10-22 | 2014-12-03 | Croda Int Plc | Polyesters |
-
2021
- 2021-08-11 CN CN202110920824.0A patent/CN113754835B/en active Active
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3219604A (en) * | 1961-07-25 | 1965-11-23 | Us Rubber Co | Polyester resin composition modified by monocarboxylic acid and metallic bridging agent |
GB942646A (en) * | 1961-07-25 | 1963-11-27 | Us Rubber Co | Polyester resin compositions |
US4343743A (en) * | 1979-12-10 | 1982-08-10 | Rhone-Poulenc Industries | Novel polyesteramides having low glass transition temperatures |
JPS6424304A (en) * | 1987-07-20 | 1989-01-26 | Toshiba Chem Corp | Resin composition material for processing transformer |
JPH02194018A (en) * | 1989-01-20 | 1990-07-31 | Kuraray Co Ltd | Polyester and resin composition for coating material |
WO2008067967A2 (en) * | 2006-12-08 | 2008-06-12 | Uniqema B.V. | Unsaturated polymers |
CN101802046A (en) * | 2007-07-12 | 2010-08-11 | 陶氏环球技术公司 | Room temperature curable polymers and precursors thereof |
CN102875785A (en) * | 2011-07-13 | 2013-01-16 | 比亚迪股份有限公司 | Polyamide modified polyester resin and preparation method thereof, and automotive primer surfacer containing polyester resin |
CN104725624A (en) * | 2013-12-23 | 2015-06-24 | 常州华科聚合物股份有限公司 | Unsaturated polyester resin for metal plate putty, and preparation method thereof |
CN104497286A (en) * | 2014-01-26 | 2015-04-08 | 南京长江涂料有限公司 | Renewable alkyd resin with high solid portion and preparation method of enamel paint |
CN106674504A (en) * | 2016-12-23 | 2017-05-17 | 仲恺农业工程学院 | Method for synthesizing unsaturated polyester by using C36 dimer fatty acid |
CN107602829A (en) * | 2017-09-19 | 2018-01-19 | 株洲时代新材料科技股份有限公司 | A kind of flexible unsaturated polyester resin and its preparation method and application |
CN107936185A (en) * | 2017-12-15 | 2018-04-20 | 仲恺农业工程学院 | A kind of modified unsaturated polyester resin and preparation method thereof |
CN111196873A (en) * | 2018-11-20 | 2020-05-26 | 万华化学集团股份有限公司 | Alkyd resin, double-crosslinked alkyd acrylate dispersion comprising alkyd resin, preparation method and application |
CN111205446A (en) * | 2020-02-28 | 2020-05-29 | 衡阳山泰化工有限公司 | High-temperature-resistant organic amine modified polyester resin and preparation method and application thereof |
CN111848935A (en) * | 2020-08-11 | 2020-10-30 | 广州德恒致远科技有限公司 | Amide group-containing biodegradable copolyester and preparation method thereof |
CN112646155A (en) * | 2020-12-21 | 2021-04-13 | 浙江光华科技股份有限公司 | Amide-modified polyester resin for powder coating and powder coating |
CN112979933A (en) * | 2021-04-07 | 2021-06-18 | 安庆瑞泰化工有限公司 | Biomass polyacid modified polyester resin and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
贺英等编著.涂料树脂化学.化学工业出版社,2007,第76-84页. * |
Also Published As
Publication number | Publication date |
---|---|
CN113754835A (en) | 2021-12-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101633729B (en) | Method for preparing unsaturated polyster resin by industrial dicyclopentadiene | |
CN103910855B (en) | A kind of vinyl ester resin and preparation method thereof | |
CN113754835B (en) | Grease-based modified unsaturated polyester resin and preparation method thereof | |
CN111825809A (en) | Ultraviolet curing resin, preparation method thereof and coating | |
CN111978444B (en) | Organic polyacid-based photocuring resin and preparation method and application thereof | |
EP0020945A1 (en) | Compositions containing half esters of organic polyols, a process for their production and use of the compositions in the production of moulded articles | |
CN105061671A (en) | Liquid photosensitive solder-resist resin for LED and preparation method thereof | |
CN111662540B (en) | Amino modified unsaturated polyester resin | |
KR101685499B1 (en) | Unsaturated polyester resin having high elongation and rigidity modulus and the method of manufacturing the same | |
CN108948338B (en) | End-capped unsaturated polyester resin and synthesis process thereof | |
CN114395089B (en) | Molded vinyl resin and preparation method thereof | |
JPS5829813A (en) | Hardenable formation composition | |
KR101375083B1 (en) | Unsaturated polyester resin having high elongation and elasticity modulus and manufacturing the same | |
JP3198833B2 (en) | Method for producing unsaturated polyester resin | |
KR20090028749A (en) | Sewerage-polyester resin concrete(prc) pipes use of recycle pet unsaturated polyester resin compound and modified polystyrene compound | |
CN111320746A (en) | Low-temperature curing polyester resin | |
JP2003096316A (en) | Process for preparing thermoset composition and reinforcing agent | |
CN110054764A (en) | A kind of synthetic method of polyester resin | |
KR102545381B1 (en) | Process of Vinylester resins for eco-friendly corrosion resistance pultrusion using recycled polyethyleneterephthalate flake | |
CN116970130A (en) | Environment-friendly unsaturated polyester resin and preparation method thereof | |
WO2023168562A1 (en) | Carbonate-containing unsaturated compound, preparation method therefor, cured product prepared therefrom, and method for degrading cured product | |
EP0064866B1 (en) | Process for the preparation of modified aromatic hydrocarbon resin | |
CN114736390A (en) | Synthesis method of block polymerization epoxy modified unsaturated resin | |
Wool | New polymers, renewables as raw materials | |
Spoljaric et al. | One-pot, mouldable, thermoplastic resins from poly (propylene carbonate) and poly (caprolactone triol) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |