CN116253985A - Glass fiber reinforced polyurethane foam plastic and preparation method thereof - Google Patents
Glass fiber reinforced polyurethane foam plastic and preparation method thereof Download PDFInfo
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- CN116253985A CN116253985A CN202310258542.8A CN202310258542A CN116253985A CN 116253985 A CN116253985 A CN 116253985A CN 202310258542 A CN202310258542 A CN 202310258542A CN 116253985 A CN116253985 A CN 116253985A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 84
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 58
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 58
- 229920003023 plastic Polymers 0.000 title claims abstract description 33
- 239000004033 plastic Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 150000003077 polyols Chemical class 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- 239000004088 foaming agent Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 30
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 26
- 239000008158 vegetable oil Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 125000004386 diacrylate group Chemical group 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920005903 polyol mixture Polymers 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000011265 semifinished product Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 37
- 238000012360 testing method Methods 0.000 description 10
- 239000006260 foam Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 2
- -1 hydroxyl compound Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
- C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
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- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/0085—Use of fibrous compounding ingredients
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- C08J2375/04—Polyurethanes
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2471/02—Polyalkylene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The invention discloses glass fiber reinforced polyurethane foam plastic and a preparation method thereof, and relates to the technical field of polyurethane foam plastic, wherein the polyurethane foam plastic comprises the following components in parts by weight: 95-135 parts of composite polyol; 60-80 parts of isocyanate; 10-20 parts of modified glass fiber; 2.5-10 parts of foaming agent; 0.3-1 part of catalyst; 1.5-5 parts of curing agent. The invention improves the traditional hard polyurethane foam plastic components and auxiliary agents, so that the auxiliary agents of the components, the base material polyol and the isocyanate have good compatibility, can be uniformly dispersed in the base material, and the formed internal closed cells are uniform, stable and firm, have good structural dimensional stability and small shrinkage, and improve the bonding strength among atoms, ions and molecules in the material to develop the glass fiber reinforced polyurethane foam plastic with excellent mechanical and physical properties.
Description
Technical Field
The invention relates to the technical field of polyurethane foam plastic, in particular to glass fiber reinforced polyurethane foam plastic and a preparation method thereof.
Background
The polyurethane foam is prepared by polymerizing and foaming isocyanate and hydroxyl compound, and the hardness of the polyurethane foam can be divided into soft and hard, wherein the hard polyurethane foam is mainly prepared from raw materials such as polyol, isocyanate, auxiliary agent and the like, and the soft polyurethane foam is mainly prepared from raw materials such as polyether polyol, polyester polyol, polyisocyanate, auxiliary agent and the like.
The rigid polyurethane foam plastic has the excellent characteristics of good heat insulation effect, light weight, large specific strength, convenient construction and the like, and also has the characteristics of sound insulation, shock resistance, electric insulation, heat resistance, cold resistance, solvent resistance and the like, and is widely used for heat insulation materials of a refrigerator body heat insulation layer of a refrigerator or a freezer, a refrigerator car and the like, heat insulation materials of buildings, storage tanks and pipelines, and a small amount of heat insulation materials are used for non-heat insulation occasions such as wood imitation, packaging materials and the like. Generally, polyurethane hard foam of lower density is mainly used as a heat insulating (heat preserving) material, and polyurethane hard foam of higher density is used as a structural material (wood-like). With the development of economy, society and science and technology, the performance of the existing rigid polyurethane foam cannot meet the application requirements, and the invention aims to provide the rigid glass fiber reinforced polyurethane foam.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the glass fiber reinforced polyurethane foam plastic which has excellent physical and mechanical properties and wide application field occasions.
In order to achieve the above object, the present invention is realized by the following technical scheme:
the glass fiber reinforced polyurethane foam plastic comprises the following components in parts by weight:
95-135 parts of composite polyol;
60-80 parts of isocyanate;
10-20 parts of modified glass fiber;
2.5-10 parts of foaming agent;
0.3-1 part of catalyst;
1.5-5 parts of curing agent.
Preferably, the composite polyol consists of vegetable oil polyol FH-4210 and vegetable oil polyol FH-2130 in mass ratio of (1-2) 1, wherein the vegetable oil polyol FH-4210 has a hydroxyl value of 200+/-10 mgKOH/g, an acid value of less than or equal to 2.0mgKOH/g, a viscosity of less than or equal to 700 (25 ℃) per cps and an average functionality of 3.8; the vegetable oil polyol FH-2130 has a hydroxyl value of 130+/-10 mgKOH/g, an acid value of less than or equal to 0.5mgKOH/g, a viscosity of less than or equal to 1200 (25 ℃)/cps and an average functionality of 2.
Preferably, the catalyst is formed by mixing pentamethyldipropylene triamine and dibutyltin dilaurate with the mass ratio of (1-1.5).
Preferably, the curing agent is formed by mixing polyethylene glycol diacrylate with the mass ratio of (3-5) being 2 and bis (2-ethylhexyl) peroxydicarbonate.
Further, the modified glass fiber is prepared by the following method: heating and pre-treating the glass fiber material, gradually heating the glass fiber material from room temperature to 280 ℃, wherein the heating rate is 10-15 ℃/min, and oxidizing the glass fiber material for 40-50min at the temperature of 280 ℃; gradually heating the glass fiber material from 280 ℃ to 420 ℃ at a heating rate of 5-10 ℃/min, and performing high-temperature treatment for 1-1.5h at the temperature of 420 ℃ to obtain glass fiber precursors; the method comprises the steps of putting glass fiber precursors into hydrofluoric acid aqueous solution with a PH value of 3 for fluorination dipping treatment, taking out the dipped glass fibers, putting the dipped glass fibers into ammonia monohydrate with a concentration of 0.45-0.55mol/L, slowly stirring for 30s, neutralizing hydrofluoric acid on the glass fibers, taking the glass fibers as anodes, carrying out an electric conduction reaction in ammonia monohydrate electrolyte solution with a concentration of 0.45-0.55mol/L for 30-40s, setting the reaction temperature to be 45-55 ℃, setting the current density of the electric conduction to be 0.25-0.35A/bundle, washing the glass fibers for 1-2 times by absolute ethyl alcohol, washing for 1-3 times by distilled water, and drying to obtain the modified glass fibers.
Preferably, the isocyanate is any one of isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
Preferably, the foaming agent is foaming agent NC-220, the foaming amount of the foaming agent is 120+/-5 ml/g, and the fineness is 10-15um.
Another object of the present invention is to provide a method for preparing a glass fiber reinforced polyurethane foam, comprising the steps of:
(1) Weighing raw material components according to parts by weight, placing the composite polyol, the foaming agent and the catalyst in a mixer, and mixing at the stirring temperature of 32-36 ℃ and the stirring rotation speed of 600-800r/min for 60-70min to obtain a polyol mixture;
(2) Placing isocyanate and modified glass fiber in a mixer, mixing at a stirring temperature of 30-32 ℃ and a stirring speed of 1000-1500r/min for 25-35min to obtain an isocyanate matrix, and treating the isocyanate matrix under ultrasonic conditions for 50-60min to enable the modified glass fiber to be uniformly dispersed in the isocyanate matrix and not agglomerated;
(3) Placing the obtained polyol mixture, isocyanate matrix and curing agent in a mixer together, stirring and mixing for 20-30min at the stirring temperature of 30-32 ℃ and the stirring rotation speed of 400-600r/min, stirring and mixing for 8-10min at the stirring temperature of 32-34 ℃ and the stirring rotation speed of 800-1000r/min, keeping the temperature, stirring and mixing for 50-60s at the stirring rotation speed of 1500-2000r/min, finally pouring the stirred reaction mixture into a mould for foaming and molding, removing the film, and placing the obtained semi-finished product into an oven for curing treatment for 10-12 hours to obtain the glass fiber reinforced polyurethane foam plastic.
The invention has the following beneficial effects: the invention improves the components and the auxiliary agents of the traditional rigid polyurethane foam plastic, so that the auxiliary agents of the components, the base material polyol and the isocyanate have good compatibility, can be uniformly dispersed in the base material, form internal closed cells which are uniform, stable and firm, have good structural dimensional stability and small shrinkage, and the bonding strength among atoms, ions and molecules in the material is improved by improving the components and the auxiliary agents, so that the glass fiber reinforced polyurethane foam plastic with excellent mechanical and physical properties is developed.
Detailed Description
The following examples are provided to illustrate the technical aspects of the present invention more clearly, but are not intended to limit the scope of the present invention.
Example 1
The polyurethane foam plastic comprises the following components in parts by weight: vegetable oil polyol FH-4210.5 parts, vegetable oil polyol FH-2130.5 parts, isophorone diisocyanate 60 parts, modified glass fiber 10 parts, foaming agent NC-220.5 parts, catalyst 0.3 parts and curing agent 1.5 parts.
In this example, the catalyst was obtained by mixing 0.15 part of pentamethyldipropylene triamine with 0.15 part of dibutyltin dilaurate; the curing agent is obtained by mixing 0.9 part of polyethylene glycol diacrylate with 0.6 part of bis (2-ethylhexyl) peroxydicarbonate.
Example 2
The polyurethane foam plastic comprises the following components in parts by weight: vegetable oil polyol FH-4210.2 parts, vegetable oil polyol FH-2130.8 parts, dicyclohexylmethane diisocyanate 65 parts, modified glass fiber 12.2 parts, foaming agent NC-220.8 parts, catalyst 0.45 parts and curing agent 2 parts.
In this example, the catalyst was obtained by mixing 0.215 parts of pentamethyldipropylene triamine with 0.235 parts of dibutyltin dilaurate; the curing agent was obtained by mixing 1.27 parts of polyethylene glycol diacrylate with 0.73 parts of bis (2-ethylhexyl) peroxydicarbonate.
Example 3
The polyurethane foam plastic comprises the following components in parts by weight: vegetable oil polyol FH-4210.9 parts, vegetable oil polyol FH-2130.49.6 parts, hexamethylene diisocyanate 70 parts, modified glass fiber 15.1 parts, foaming agent NC-220.6 parts, catalyst 0.65 parts and curing agent 3.4 parts.
In this example, the catalyst was obtained by mixing 0.28 part of pentamethyldipropylene triamine with 0.37 part of dibutyltin dilaurate; the curing agent is obtained by mixing 2.3 parts of polyethylene glycol diacrylate with 1.1 parts of bis (2-ethylhexyl) peroxydicarbonate.
Example 4
The polyurethane foam plastic comprises the following components in parts by weight: vegetable oil polyol FH-4210.0 parts, vegetable oil polyol FH-2130.47.6 parts, isophorone diisocyanate 76.4 parts, modified glass fiber 18.2 parts, foaming agent NC-220 8 parts, catalyst 0.85 parts and curing agent 4.2 parts.
In this example, the catalyst was obtained by mixing 0.35 part of pentamethyldipropylene triamine with 0.50 part of dibutyltin dilaurate; the curing agent was obtained by mixing 2.93 parts of polyethylene glycol diacrylate with 1.27 parts of bis (2-ethylhexyl) peroxydicarbonate.
Example 5
The polyurethane foam plastic comprises the following components in parts by weight: vegetable oil polyol FH-4210 90, vegetable oil polyol FH-2130 45, dicyclohexylmethane diisocyanate 80, modified glass fiber 20, foaming agent NC-220, catalyst 1 and curing agent 5.
In this example, the catalyst was obtained by mixing 0.4 part of pentamethyldipropylene triamine with 0.6 part of dibutyltin dilaurate; the curing agent was obtained by mixing 3.57 parts of polyethylene glycol diacrylate with 1.43 parts of bis (2-ethylhexyl) peroxydicarbonate.
In the embodiments 1 to 5 of the present invention, the modified glass fiber is prepared by the following method: heating and pre-treating the glass fiber material, gradually heating the glass fiber material from room temperature to 280 ℃, wherein the heating rate is 10-15 ℃/min, and oxidizing the glass fiber material for 40-50min at the temperature of 280 ℃; gradually heating the glass fiber material from 280 ℃ to 420 ℃ at a heating rate of 5-10 ℃/min, and performing high-temperature treatment for 1-1.5h at the temperature of 420 ℃ to obtain glass fiber precursors; the method comprises the steps of putting glass fiber precursors into hydrofluoric acid aqueous solution with a PH value of 3 for fluorination dipping treatment, taking out the dipped glass fibers, putting the dipped glass fibers into ammonia monohydrate with a concentration of 0.45-0.55mol/L, slowly stirring for 30s, neutralizing hydrofluoric acid on the glass fibers, taking the glass fibers as anodes, carrying out an electric conduction reaction in ammonia monohydrate electrolyte solution with a concentration of 0.45-0.55mol/L for 30-40s, setting the reaction temperature to be 45-55 ℃, setting the current density of the electric conduction to be 0.25-0.35A/bundle, washing the glass fibers for 1-2 times by absolute ethyl alcohol, washing for 1-3 times by distilled water, and drying to obtain the modified glass fibers.
It is worth noting that: the vegetable oil polyol FH-4210 and the vegetable oil polyol FH-2130 in the embodiment of the invention are purchased from the field harbor city aviation technology Co., ltd, and the physicochemical performance indexes of the vegetable oil polyol FH-4210 and the vegetable oil polyol FH-2130 are shown in the following tables 1 and 2:
table 1: vegetable oil polyol FH-4210
| Appearance of | Light yellow transparent liquid without impurity |
| Hydroxyl value (mgKOH/g) | 200±10 |
| Acid value (mgKOH/g) | ≤2.0 |
| Viscosity (25 ℃ C.)/cps | ≤700 |
| Moisture% (weight) | ≤0.1 |
| Average functionality of | 3.8 |
Table 2: vegetable oil polyol FH-2130
| Appearance of | Light yellow transparent liquid without impurity |
| Hydroxyl value (mgKOH/g) | 130±10 |
| Acid value (mgKOH/g) | ≤0.5 |
| Viscosity (25 ℃ C.)/cps | ≤1200 |
| Moisture% (weight) | ≤0.1 |
| Average functionality of | 2 |
In addition, the foaming agent described in the examples of the present invention was obtained from NC-220, a foaming agent available from Zhejiang rubber and plastic technologies Co., ltd, and the product data of the foaming agent is shown in Table 3 below:
table 3: foaming agent NC-220 product data
| Appearance of | Decomposition temperature | Gas generation amount | Fineness of |
| White powder | 220℃ | 120±5ml/g | 10-15um |
The embodiment provides a preparation method of glass fiber reinforced polyurethane foam plastic aiming at the components in the embodiments 1-5, which comprises the following specific steps: weighing raw material components according to parts by weight, placing the composite polyol, the foaming agent and the catalyst in a mixer, and mixing at the stirring temperature of 32-36 ℃ and the stirring rotation speed of 600-800r/min for 60-70min to obtain a polyol mixture; placing isocyanate and modified glass fiber in a mixer, mixing at a stirring temperature of 30-32 ℃ and a stirring speed of 1000-1500r/min for 25-35min to obtain an isocyanate matrix, and treating the isocyanate matrix under ultrasonic conditions for 50-60min to enable the modified glass fiber to be uniformly dispersed in the isocyanate matrix and not agglomerated; placing the obtained polyol mixture, isocyanate matrix and curing agent in a mixer together, stirring and mixing for 20-30min at the stirring temperature of 30-32 ℃ and the stirring rotation speed of 400-600r/min, stirring and mixing for 8-10min at the stirring temperature of 32-34 ℃ and the stirring rotation speed of 800-1000r/min, keeping the temperature, stirring and mixing for 50-60s at the stirring rotation speed of 1500-2000r/min, finally pouring the stirred reaction mixture into a mould for foaming and molding, removing the film, and placing the obtained semi-finished product into an oven for curing for 10-12 hours to obtain the glass fiber reinforced polyurethane foam plastic of the embodiment.
Comparative example 1
A polyurethane foam differing from example 3 in that:
the polyol in comparative example 1 was only polyoxypropylene diol, and other conditions were the same.
Comparative example 2
A polyurethane foam differing from example 4 in that:
the polyol in comparative example 2 was polytetrahydrofuran diol only, and other conditions were the same.
Comparative example 3
A polyurethane foam differing from example 5 in that:
the glass fiber in comparative example 3 was not modified and not treated, and other conditions were the same.
Comparative example 4
A polyurethane foam differing from example 3 in that:
the blowing agent in comparative example 4 was water, and other conditions were the same.
Comparative example 5
A polyurethane foam differing from example 4 in that:
the catalyst in comparative example 5 was only dibutyltin dilaurate, and the other conditions were the same.
Comparative example 6
A polyurethane foam differing from example 4 in that:
the catalyst in comparative example 6 was obtained by uniformly mixing pentamethyldipropylenetriamine and dibutyltin dilaurate in a mass ratio of 1:1, and other conditions were the same.
Comparative example 7
A polyurethane foam differing from example 5 in that:
the curing agent in comparative example 7 was polyethylene glycol diacrylate alone, and other conditions were the same.
Comparative example 8
A polyurethane foam differing from example 5 in that:
the curing agent in comparative example 8 is obtained by uniformly mixing polyethylene glycol diacrylate and bis (2-ethylhexyl) peroxydicarbonate in a mass ratio of 1:1, and other condition factors are the same.
Test examples
The polyurethane foams prepared in examples 1 to 5 and comparative examples 1 to 8 were cut into standard samples for performance test, and the preparation of the samples should be performed 7 days after the production of the products. The original skin of the material was removed and sampled from the foam interior. The anisotropic foam is sampled parallel to the foam expansion direction and perpendicular to the foam expansion direction, respectively. The compressive modulus test specimen and the tensile strength test specimen are preferably processed by a die cutter.
In addition, according to the specification of GB/T2918, under the conditions that the temperature is 23+/-2 ℃ and the relative humidity is 45% -65%, the test sample is subjected to 24-hour state adjustment, and then the physical property and mechanical property test is carried out.
Specifically, each property of the material was tested according to the following method, and the test results are shown in table 4:
(1) Apparent core Density/(. Times.10) 3 kg/m 3 )
The test was carried out as specified in GB/T6343.
(2) Compressive Strength/Mpa, modulus of elasticity/Mpa
The test was performed as specified by GJB 1585. If the yield point occurs before the relative deformation is 10%, the stress of the yield point is the compressive strength, otherwise, the compressive stress at the relative deformation of 10% is defined as the compressive strength.
(3) Dimensional stability/(70 ℃,48 h)%
The test was carried out as specified in GB/T8811.
(4) Tensile strength/Mpa, impact strength/Mpa, flexural strength/Mpa and flexural modulus/(mJ/mm) 3 )
Testing was performed as specified by GJB 1585.
Table 4: performance parameters of examples and comparative examples
As is clear from the analysis of Table 4 above, the polyurethane foam of the examples of the present invention was approximately at 0.25.+ -. 0.01X10 in terms of apparent core density of physical properties 3 kg/m 3 Is suitable for bearing light load, heat insulation, shock absorption, structural materials, sandwich structures and other purposes; in physical propertiesIn terms of dimensional stability, the polyurethane foam plastics prepared in the embodiments 1-5 of the invention have the dimensional stability of less than or equal to 1.5%, the comparative examples have the poor dimensional stability of less than 2.0% due to the change of the mass ratio of the components and part of the auxiliary agents, the preferred embodiment of the invention is the embodiment 5, the dimensional stability is 1.3%, the preferred embodiment of the invention is the embodiment 4, the dimensional stability is 1.2%, and the preferred embodiment is improved by 1.0-2.3% compared with the comparative example.
In terms of compression strength of mechanical properties, the preferred embodiment 5 of the invention can reach 9.5Mpa, the most preferred embodiment 4 can reach 10.3Mpa, and the most preferred embodiment is improved by 17.4-203.6% compared with the comparative example, wherein the influence of the glass fiber unmodified untreated comparative example 3 is the greatest, the compression strength of the obtained polyurethane foam plastic is the least, and the influence of the pentamethyldipropylenetriamine and the dibutyl tin dilaurate in the mass ratio of 1:1 is the least;
in terms of compression elastic modulus of mechanical properties, the better example 5 of the invention can reach 343Mpa, the best example 4 can reach 351Mpa, and the best example is improved by 15.7-205.2% compared with the comparative example, wherein the influence of the glass fiber unmodified untreated comparative example 3 is the largest, the compression elastic modulus of the obtained material is the smallest, and the influence of the catalyst of pentamethyldipropylenetriamine and dibutyltin dilaurate with the mass ratio of 1:1 is the smallest in comparative example 6;
in terms of tensile strength of mechanical properties, the tensile strength of the polyurethane foam plastic can reach 7.2Mpa, the tensile strength of the polyurethane foam plastic can reach 7.3Mpa, the tensile strength of the polyurethane foam plastic can reach 30.3-143.3% higher than that of the comparative example, wherein the influence of the unmodified and untreated glass fiber in the comparative example 3 is the greatest, and the influence of the curing agent of polyethylene glycol diacrylate and bis (2-ethylhexyl) peroxydicarbonate in the mass ratio of 1:1 in the comparative example 8 is the least;
in terms of impact strength of mechanical properties, the preferred embodiment 5 and the preferred embodiment 4 of the invention can reach 2.2mJ/mm 3 Which is improved by 22.2 to 210.0% compared with the comparative example, wherein the impact of the unmodified, untreated comparative example 3 of the glass fibers is greatest and the resulting material is punched outThe impact strength is minimum, and the influence of comparative example 8 of polyethylene glycol diacrylate and bis (2-ethylhexyl) peroxydicarbonate curing agent with the mass ratio of 1:1 and comparative example 6 of pentamethyldipropylene triamine and dibutyltin dilaurate catalyst with the mass ratio of 1:1 is minimum;
in the bending strength of mechanical properties, the bending strength of the polyurethane foam plastic can reach 9.3Mpa, the bending strength of the polyurethane foam plastic can reach 9.5Mpa, the bending strength of the polyurethane foam plastic can reach 21.7-143.5% compared with the comparative example, wherein the influence of the glass fiber unmodified untreated comparative example 3 is the largest, and the influence of the catalyst of pentamethyldipropylene triamine and dibutyltin dilaurate with the mass ratio of 1:1 is the smallest;
in terms of flexural modulus of mechanical properties, the better example 5 of the invention can reach 268Mpa, the best example 4 can reach 273Mpa, and the best example is improved by 17.6.7-120.1% compared with the comparative example, wherein the influence of the glass fiber unmodified untreated comparative example 3 is the largest, the flexural modulus of the obtained material is the smallest, and the influence of the polyethylene glycol diacrylate and the curing agent of bis (2-ethylhexyl) peroxydicarbonate with the mass ratio of 1:1 is the smallest in comparative example 8.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The glass fiber reinforced polyurethane foam plastic is characterized by comprising the following components in parts by weight:
95-135 parts of composite polyol;
60-80 parts of isocyanate;
10-20 parts of modified glass fiber;
2.5-10 parts of foaming agent;
0.3-1 part of catalyst;
1.5-5 parts of curing agent.
2. The glass fiber reinforced polyurethane foam according to claim 1, wherein the composite polyol is composed of vegetable oil polyol FH-4210 and vegetable oil polyol FH-2130 in a mass ratio of (1-2) 1, and the vegetable oil polyol FH-4210 has a hydroxyl value of 200+ -10 mgKOH/g, an acid value of 2.0mgKOH/g or less, a viscosity of 700 (25 ℃) per cps or less, and an average functionality of 3.8; the vegetable oil polyol FH-2130 has a hydroxyl value of 130+/-10 mgKOH/g, an acid value of less than or equal to 0.5mgKOH/g, a viscosity of less than or equal to 1200 (25 ℃)/cps and an average functionality of 2.
3. The glass fiber reinforced polyurethane foam according to claim 2, wherein the catalyst is composed of a mixture of pentamethyldipropylene triamine and dibutyltin dilaurate in a mass ratio of 1 (1-1.5).
4. The glass fiber reinforced polyurethane foam according to claim 3, wherein the curing agent is composed of polyethylene glycol diacrylate and bis (2-ethylhexyl) peroxydicarbonate in a mass ratio of (3-5): 2.
5. The glass fiber reinforced polyurethane foam of claim 4, wherein the modified glass fiber is prepared by the process of: heating and pre-treating the glass fiber material, gradually heating the glass fiber material from room temperature to 280 ℃, wherein the heating rate is 10-15 ℃/min, and oxidizing the glass fiber material for 40-50min at the temperature of 280 ℃; gradually heating the glass fiber material from 280 ℃ to 420 ℃ at a heating rate of 5-10 ℃/min, and performing high-temperature treatment for 1-1.5h at the temperature of 420 ℃ to obtain glass fiber precursors; the method comprises the steps of putting glass fiber precursors into hydrofluoric acid aqueous solution with a PH value of 3 for fluorination dipping treatment, taking out the dipped glass fibers, putting the dipped glass fibers into ammonia monohydrate with a concentration of 0.45-0.55mol/L, slowly stirring for 30s, neutralizing hydrofluoric acid on the glass fibers, taking the glass fibers as anodes, carrying out an electric conduction reaction in ammonia monohydrate electrolyte solution with a concentration of 0.45-0.55mol/L for 30-40s, setting the reaction temperature to be 45-55 ℃, setting the current density of the electric conduction to be 0.25-0.35A/bundle, washing the glass fibers for 1-2 times by absolute ethyl alcohol, washing for 1-3 times by distilled water, and drying to obtain the modified glass fibers.
6. The glass fiber reinforced polyurethane foam of claim 1, wherein the isocyanate is any one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate.
7. The glass fiber reinforced polyurethane foam according to claim 1, wherein the foaming agent is foaming agent NC-220, and the foaming amount of the foaming agent is 120+/-5 ml/g, and the fineness is 10-15um.
8. The glass fiber reinforced polyurethane foam of claim 1, comprising the following components in parts by weight:
129.6 parts of composite polyol;
76.4 parts of isocyanate;
18.2 parts of modified glass fiber;
8 parts of foaming agent;
0.85 parts of catalyst;
4.2 parts of curing agent;
the composite polyol consists of vegetable oil polyol FH-4210 and vegetable oil polyol FH-2130 according to a mass ratio of 1.72:1.
9. The glass fiber reinforced polyurethane foam according to claim 8, wherein the catalyst is composed of a mixture of pentamethyldipropylene triamine and dibutyltin dilaurate in a mass ratio of 1:1.41; the curing agent is formed by mixing polyethylene glycol diacrylate with the mass ratio of 4.6:2 and bis (2-ethylhexyl) peroxydicarbonate.
10. A process for the preparation of a polyurethane foam as claimed in claim 1, comprising the steps of:
(1) Weighing raw material components according to parts by weight, placing the composite polyol, the foaming agent and the catalyst in a mixer, and mixing at the stirring temperature of 32-36 ℃ and the stirring rotation speed of 600-800r/min for 60-70min to obtain a polyol mixture;
(2) Placing isocyanate and modified glass fiber in a mixer, mixing at a stirring temperature of 30-32 ℃ and a stirring speed of 1000-1500r/min for 25-35min to obtain an isocyanate matrix, and treating the isocyanate matrix under ultrasonic conditions for 50-60min to enable the modified glass fiber to be uniformly dispersed in the isocyanate matrix and not agglomerated;
placing the obtained polyol mixture, isocyanate matrix and curing agent in a mixer together, stirring and mixing for 20-30min at the stirring temperature of 30-32 ℃ and the stirring rotation speed of 400-600r/min, stirring and mixing for 8-10min at the stirring temperature of 32-34 ℃ and the stirring rotation speed of 800-1000r/min, keeping the temperature, stirring and mixing for 50-60s at the stirring rotation speed of 1500-2000r/min, finally pouring the stirred reaction mixture into a mould for foaming and molding, removing the film, and placing the obtained semi-finished product into an oven for curing treatment for 10-12 hours to obtain the glass fiber reinforced polyurethane foam plastic.
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