CN113121775B - High-temperature-resistant light high-strength heat-insulating material and preparation method thereof - Google Patents
High-temperature-resistant light high-strength heat-insulating material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011810 insulating material Substances 0.000 title claims abstract description 24
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 50
- 239000004917 carbon fiber Substances 0.000 claims abstract description 50
- 150000001721 carbon Chemical class 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 58
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 32
- 229920000570 polyether Polymers 0.000 claims description 32
- 229920005862 polyol Polymers 0.000 claims description 29
- 150000003077 polyols Chemical class 0.000 claims description 29
- 239000012948 isocyanate Substances 0.000 claims description 20
- 150000002513 isocyanates Chemical class 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012774 insulation material Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- 239000004970 Chain extender Substances 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 229920005906 polyester polyol Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical group FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical group CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000185 sucrose group Chemical group 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 27
- 229920005830 Polyurethane Foam Polymers 0.000 description 9
- 239000011496 polyurethane foam Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08G2101/00—Manufacture of cellular products
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a high-temperature-resistant light high-strength heat-insulating material, which is characterized in that modified hydroxylated carbon fibers are added into raw materials of the heat-insulating material, the hydroxylated carbon fibers and the heat-insulating material have better composite property, and the hydroxylated carbon fibers are matched with other components limited by the invention, so that the high-temperature resistance and the mechanical property of the heat-insulating material can be improved. The invention also provides a preparation method of the heat-insulating material.
Description
Technical Field
The invention relates to a high-temperature-resistant light high-strength heat-insulating material and a preparation method thereof.
Background
The polyurethane foam is obtained by mixing the polyol component and the isocyanate component according to a certain proportion, has the excellent characteristics of good heat insulation effect, light weight, large specific strength, convenient construction and the like, 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 refrigerator bodies of refrigerators and freezers, cold storages, refrigerated trucks and the like, buildings, storage tanks, pipelines and the like. With the continuous development of society, the performance requirements of people on the heat insulation material are gradually improved, the actual heat conductivity coefficient of the traditional polyurethane foam heat insulation material is about 0.03W/mK, the high temperature resistance is poor, and the like, and the performances in all aspects need to be further improved.
Therefore, it is desirable to provide a high temperature resistant, lightweight, and high strength thermal insulation material to overcome the problems of the prior art.
Disclosure of Invention
The invention provides a high-temperature-resistant light high-strength heat-insulating material, wherein modified hydroxylated carbon fibers are added into the raw materials of the heat-insulating material, the hydroxylated carbon fibers and the heat-insulating material have better composite property, and the modified hydroxylated carbon fibers are matched with other components defined by the invention, so that the high-temperature resistance and the mechanical property of the heat-insulating material can be improved. The invention also provides a preparation method of the heat-insulating material.
The above purpose of the invention is realized by the following technical scheme:
a high-temperature-resistant light high-strength heat-insulating material is obtained by reacting an isocyanate component and an isocyanate-reactive component;
the isocyanate component is polyphenyl methane polyisocyanate;
the isocyanate reactive component comprises polyester polyol, polyether polyol, a chain extender, a stabilizer, a foaming agent, a flame retardant, a catalyst, a foam stabilizer and hydroxylated carbon fibers;
the preparation method of the hydroxylated carbon fiber comprises the following steps: adding concentrated nitric acid and concentrated sulfuric acid into a reactor, controlling the temperature of the reactor to be 80-100 ℃, starting stirring, adding carbon fibers with the length of 5-10 mm, reacting for 2-4 hours, discharging, washing with distilled water, and drying to obtain oxidized carbon fibers; adding thionyl chloride and the oxidized carbon fibers into a reactor, controlling the temperature of the reactor to be 65-75 ℃, starting stirring, reacting for 15-20 hours, discharging, washing with anhydrous tetrahydrofuran, and drying to obtain chlorinated carbon fibers; and step three, adding 4-dimethylpyridine, N-dimethylformamide, 1, 4-butanediol and the chlorinated carbon fibers into a reactor, controlling the temperature of the reactor to be 75-85 ℃, starting stirring, reacting for 30-35 hours, discharging, washing with anhydrous tetrahydrofuran, and drying to obtain the hydroxylated carbon fibers.
The invention adopts the chopped carbon fibers as the material for reinforcing the polyurethane foam so as to improve various performances of the polyurethane foam. However, the material performance cannot be significantly improved by adding the conventional carbon fiber into the reaction system of the traditional polyurethane foam, but the final material performance is reduced because the carbon fiber is not easy to disperse and the compounding property with polyurethane molecules is not good. According to the invention, a great deal of research shows that the hydroxylated carbon fiber obtained by oxidizing, chlorinating and hydroxylating the carbon fiber and finally grafting hydroxyl onto the surface of the carbon fiber by using 1, 4-butanediol as a grafting monomer can improve various performances of the heat-insulating material when added into the preparation of polyurethane foam.
The composition comprises the following components in parts by mass:
the using amount of the polyester polyol is 30-50 parts by mass;
the using amount of the polyether polyol is 30-50 parts by mass;
the using amount of the chain extender is 1-3 parts by mass;
the dosage of the stabilizer is 0.5 to 2 parts by mass;
the amount of the foaming agent is 5-15 parts by mass;
the dosage of the flame retardant is 1 to 3 parts by mass;
the dosage of the catalyst is 0.1-1 part by mass;
the dosage of the foam stabilizer is 1-2 parts by mass;
the amount of the hydroxylated carbon fiber is 10 to 15 parts by mass.
The mass of the isocyanate component and the isocyanate reactive component is 1-1.3: 1.
preferably, the polyester polyol has a hydroxyl value of 150 to 400mgKOH/g, and is preferably prepared by polycondensation of phthalic anhydride and diethylene glycol, and the hydroxyl value is 315mgKOH/g; the polyether polyol comprises:
polyether polyol 1, the initiator is glycerol, the hydroxyl value is 560mgKOH/g, the polyether polyol is prepared by propylene oxide polymerization and ethylene oxide end capping, the dosage of the ethylene oxide accounts for 15 percent of the total mass of the polymerization monomers,
polyether glycol 2, sucrose as initiator and hydroxyl value of 420mgKOH/g, propylene oxide homopolymerization,
polyether polyol 3, sorbitol as an initiator, 500mgKOH/g of hydroxyl value, and propylene oxide.
Preferably, the following components are calculated according to relative parts by mass: the using amount of the polyether glycol 1 is 1-2 parts by mass; the using amount of the polyether polyol 2 is 15-18 parts by mass; the using amount of the polyether polyol 3 is 18-20 parts by mass.
In the preferable technical scheme of the invention, the types and the use amounts of the raw materials of the heat-insulating material, particularly the types and the use amounts of the polyester polyol and the polyether polyol are controlled, so that the prepared heat-insulating material has better mechanical properties.
The chain extender comprises trimethylolpropane and pentaerythritol, and preferably, the mass ratio of the trimethylolpropane to the pentaerythritol is 3:1. the preferable chain extender is a compounded chain extender of trimethylolpropane and pentaerythritol, and the proportion of the two chain extenders is controlled, so that the crosslinking degree of the prepared polyurethane foam is in a proper range, and the heat-insulating material has excellent mechanical properties.
In the first step of the preparation method of the hydroxylated carbon fiber, the following components are calculated in parts by mass: the using amount of the concentrated nitric acid is 40-50 parts by mass, the using amount of the concentrated sulfuric acid is 100-120 parts by mass, and the using amount of the carbon fiber is 10-20 parts by mass;
in the second step of the preparation method of the hydroxylated carbon fiber, the following components are calculated according to relative parts by mass: the dosage of the thionyl chloride is 100 parts by mass, and the dosage of the oxidized carbon fiber is 5-8 parts by mass;
in the third step of the preparation method of the hydroxylated carbon fiber, the following components are calculated according to relative parts by mass: the content of the 4-lutidine is 1-3 parts by mass, the content of the N, N-dimethylformamide is 40-50 parts by mass, the content of the 1, 4-butanediol is 40-50 parts by mass, and the content of the chlorinated carbon fiber is 10-20 parts by mass.
1, 4-butanediol is selected as the micromolecule monomer for introducing hydroxyl, because the 1, 4-butanediol has proper chain length, the dispersibility of the carbon fiber can be improved to a small extent, and the 1, 4-butanediol has good reactivity with isocyanate groups, and finally, various performances of the heat insulation material are improved.
The stabilizer is propylene carbonate, the foaming agent is pentafluoropropane, the flame retardant is triethyl phosphate, and the catalyst is one or more of N, N-dimethylcyclohexylamine, triethylene diamine and bis (dimethylaminoethyl) ether.
The chemical substances which are not described in the invention can be prepared from commercial products or conventional technical schemes and conventional technical parameters, and the implementation of the invention is not influenced.
The preparation method of the heat insulation material comprises the steps of controlling the temperature of the isocyanate component and the isocyanate reactive component to be 25-35 ℃, adding the isocyanate reactive component into a high-pressure foaming machine, injecting the mixture into a mold, demolding, and curing to obtain the heat insulation material; wherein the pressure of a gun head of the high-pressure foaming machine is 135-145 bar, and the temperature of a mould is controlled to be 40-45 ℃.
The invention has the following beneficial effects: according to the invention, the special hydroxylated carbon fiber is added in the preparation of the polyurethane foam, and the variety and the dosage of partial raw materials for synthesizing the polyurethane foam are controlled, so that the prepared heat-insulating material has the beneficial effects of better high-temperature resistance, mechanical property, lower heat conductivity coefficient and the like.
It should be noted that the contents of the present invention that are not described can be performed with reference to the technical solutions commonly used in the art, and the implementation of the present invention is not affected.
Detailed Description
The invention is further illustrated by the following examples. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
The examples and comparative examples used the following starting materials:
isocyanate component, polyphenyl methane polyisocyanate, brand PM200, vanhua chemical production;
polyester polyol, which is obtained by polycondensation of phthalic anhydride and diethylene glycol and has a hydroxyl value of 315mgKOH/g;
polyether polyol 1, wherein the initiator is glycerol, the hydroxyl value is 560mgKOH/g, and the polyether polyol is prepared by polymerizing propylene oxide and blocking ethylene oxide;
polyether polyol 2, wherein the initiator is sucrose, the hydroxyl value is 420mgKOH/g, and the propylene oxide is homopolymerized;
polyether polyol 3, wherein the initiator is sorbitol, the hydroxyl value is 500mgKOH/g, and the propylene oxide is homopolymerized;
carbon fiber, brand T300, produced by shanxi coal gasification in chinese academy of sciences;
stabilizers, propylene carbonate;
a blowing agent, pentafluoropropane;
flame retardant, triethyl phosphate;
catalyst, triethylene diamine;
foam stabilizer, brand B8545, produced by winning company.
The starting materials not described in the examples and comparative examples are from conventional commercial products.
The preparation method of the combined polyether 1 comprises the following steps: and (2) uniformly mixing 1 part by mass of polyether polyol 1, 15 parts by mass of polyether polyol 2 and 18 parts by mass of polyether polyol 3 at room temperature.
The preparation method of the combined polyether 2 comprises the following steps: and (2) uniformly mixing 2 parts by mass of polyether polyol 1, 18 parts by mass of polyether polyol 2 and 20 parts by mass of polyether polyol 3 at room temperature.
The preparation method of the composite chain extender comprises the following steps: at room temperature, mixing trimethylolpropane and pentaerythritol according to a mass ratio of 3:1, and uniformly mixing to obtain the product.
Hydroxylated carbon fibers with different lengths are obtained by chopping the T300 carbon fibers.
The preparation methods of the hydroxylated carbon fiber 1, the hydroxylated carbon fiber 2 and the comparative hydroxylated carbon fibers 1 to 3 are as follows: adding concentrated nitric acid and concentrated nitric acid into a reactor, controlling the temperature of the reactor to be 80 ℃, starting stirring, adding carbon fibers, reacting for 4 hours, discharging, washing with distilled water, and drying to obtain oxidized carbon fibers; adding thionyl chloride and the oxidized carbon fibers into a reactor, controlling the temperature of the reactor to be 65 ℃, starting stirring, discharging after reacting for 20 hours, washing with anhydrous tetrahydrofuran, and drying to obtain chlorinated carbon fibers; and step three, adding 4-dimethylpyridine, N-dimethylformamide, 1, 4-butanediol (raw materials in the comparative hydroxylated carbon fiber 3 are replaced by ethylene glycol) and the chlorinated carbon fiber into a reactor, controlling the temperature of the reactor to be 75 ℃, starting stirring, reacting for 35 hours, discharging, washing with anhydrous tetrahydrofuran, and drying to obtain the hydroxylated carbon fiber.
The specific types and amounts of the different raw materials in the production processes of the hydroxylated carbon fiber 1, the hydroxylated carbon fiber 2 and the comparative hydroxylated carbon fibers 1 to 3 are shown in tables 1, 2 and 3, respectively, in terms of the relative parts by mass of the raw materials in each specific step.
Table 1 dosage (parts by mass) of each raw material in step one of preparation method of hydroxylated carbon fiber
| Categories | Oxidized carbon fiber 1 | Oxidized carbon fiber 2 | Comparative oxidized carbon fiber 1 | Comparative oxidized carbon fiber 2 |
| Concentrated sulfuric acid | 100 | 120 | 120 | 120 |
| Concentrated nitric acid | 40 | 50 | 50 | 50 |
| 5mm carbon fiber | 10 | |||
| 10mm carbon fiber | 20 | |||
| 3mm carbon fiber | 20 | |||
| 15mm carbon fiber | 20 |
TABLE 2 consumption of raw materials (parts by mass) in step two of the preparation method of hydroxylated carbon fibers
| Categories | Chlorinated carbon fiber 1 | Chlorinated carbon fiber 2 | Comparative chlorinated carbon fiber 1 | Comparative chlorinated carbon fiber 2 |
| Thionyl chloride | 100 | 100 | 100 | 100 |
| Oxidized carbon fiber 1 | 5 | |||
| Oxidized carbon fiber 2 | 8 | |||
| Comparative oxidized carbon fiber 1 | 8 | |||
| Comparative oxidized carbon fiber 2 | 8 |
TABLE 3 consumption of raw materials (in parts by mass) in the three steps of the preparation method of hydroxylated carbon fibers
The isocyanate-reactive component is prepared by the following method: the raw materials were mixed uniformly at room temperature according to the type and amount of raw materials in table 4 to obtain the corresponding isocyanate-reactive component.
TABLE 4 amounts (parts by mass) of raw materials in the preparation of isocyanate-reactive component
Preparation method of insulating material of examples and comparative examples: at 30 ℃, mixing an isocyanate component and an isocyanate reactive component according to a mass ratio of 1.3:1, adding the mixture into a high-pressure foaming machine, injecting the mixture into a mold, demolding after 2 hours, and curing at 25 ℃ for 24 hours to obtain a heat-insulating material; wherein the pressure of a gun head of the high-pressure foaming machine is 145bar, and the temperature of a mould is controlled at 45 ℃. Insulation samples prepared from isocyanate-reactive component 1, isocyanate-reactive component 2, comparative isocyanate-reactive component 1, comparative isocyanate-reactive component 2, comparative isocyanate-reactive component 3, comparative isocyanate-reactive component 4 correspond to example 1, example 2, comparative example 1, comparative example 2, comparative example 3, comparative example 4, respectively.
The examples and comparative samples were tested for performance:
the heat conductivity coefficient test standard is GB/T3399-1982;
the compression strength test standard is GB/T8813-1988;
the tensile strength test standard is GB/T9641-1988;
the size change rate test standard at 85 ℃ is GB/T8811-2008.
The results of the performance tests of the examples and comparative examples are shown in Table 5.
TABLE 5 results of performance testing of examples and comparative examples
| Categories | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Thermal conductivity W/m.K (25 ℃ C.) | 0.0165 | 0.0158 | 0.0195 | 0.0188 | 0.0221 | 0.0182 |
| Strong compressionDegree Kpa | 822 | 853 | 625 | 687 | 693 | 717 |
| Tensile Strength Kpa | 966 | 990 | 675 | 720 | 744 | 810 |
| Dimensional change rate at 85 DEG C | 2.3％ | 1.5％ | 4％ | 3.3％ | 3.5％ | 3.1％ |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A high-temperature-resistant light high-strength heat-insulating material is characterized in that the material is obtained by reacting an isocyanate component and an isocyanate-reactive component;
the isocyanate component is polyphenyl methane polyisocyanate;
the isocyanate reactive component comprises polyester polyol, polyether polyol, a chain extender, a stabilizer, a foaming agent, a flame retardant, a catalyst, a foam stabilizer and hydroxylated carbon fibers;
the preparation method of the hydroxylated carbon fiber comprises the following steps: adding concentrated nitric acid and concentrated sulfuric acid into a reactor, controlling the temperature of the reactor to be 80-100 ℃, starting stirring, adding carbon fibers with the length of 5-10mm, reacting for 2-4 hours, discharging, washing with distilled water, and drying to obtain oxidized carbon fibers; adding thionyl chloride and the oxidized carbon fiber into a reactor, controlling the temperature of the reactor to be 65-75 ℃, starting stirring, discharging after reacting for 15-20 hours, washing with anhydrous tetrahydrofuran and drying to obtain the chlorinated carbon fiber; adding 4-dimethylpyridine, N-dimethylformamide, 1, 4-butanediol and the chlorinated carbon fiber into a reactor, controlling the temperature of the reactor to be 75-85 ℃, starting stirring, reacting for 30-35 hours, discharging, washing with anhydrous tetrahydrofuran and drying to obtain a hydroxylated carbon fiber;
the composition comprises the following components in parts by mass:
the using amount of the polyester polyol is 30 to 50 parts by mass;
the using amount of the polyether polyol is 30 to 50 parts by mass;
the using amount of the chain extender is 1 to 3 parts by mass;
the dosage of the hydroxylated carbon fiber is 10 to 15 parts by mass;
the mass ratio of the isocyanate component to the isocyanate-reactive component is 1 to 1.3:1;
the chain extender consists of trimethylolpropane and pentaerythritol;
in the first step of the preparation method of the hydroxylated carbon fiber, the following components are calculated in parts by mass: the using amount of the concentrated nitric acid is 40 to 50 parts by mass, the using amount of the concentrated sulfuric acid is 100 to 120 parts by mass, and the using amount of the carbon fiber is 10 to 20 parts by mass;
in the second step of the preparation method of the hydroxylated carbon fiber, the following components are calculated according to the relative parts by mass: the using amount of the thionyl chloride is 100 parts by mass, and the using amount of the oxidized carbon fiber is 5 to 8 parts by mass;
in the third step of the preparation method of the hydroxylated carbon fiber, the following components are calculated according to relative parts by mass: the amount of the 4-dimethylpyridine is 1 to 3 parts by mass, the amount of the N, N-dimethylformamide is 40 to 50 parts by mass, the amount of the 1, 4-butanediol is 40 to 50 parts by mass, and the amount of the chlorinated carbon fiber is 10 to 20 parts by mass.
2. The thermal insulation material according to claim 1, characterized in that the following components are calculated in relative parts by mass:
the dosage of the stabilizer is 0.5 to 2 parts by mass;
the using amount of the foaming agent is 5 to 15 parts by mass;
the using amount of the flame retardant is 1 to 3 parts by mass;
the dosage of the catalyst is 0.1 to 1 part by mass;
the using amount of the foam stabilizer is 1 to 2 parts by mass.
3. The thermal insulation material as claimed in claim 1, wherein the hydroxyl value of the polyester polyol is 150 to 400mgKOH/g; the polyether polyol comprises:
polyether polyol 1, glycerol as an initiator, 560mgKOH/g of hydroxyl value, propylene oxide polymerization and ethylene oxide end capping,
polyether polyol 2, the initiator is sucrose, the hydroxyl value is 420mgKOH/g, propylene oxide homopolymerizes to get final product, polyether polyol 3, the initiator is sorbitol, the hydroxyl value is 500mgKOH/g, propylene oxide homopolymerizes to get final product.
4. The insulating material according to claim 3, wherein the polyester polyol is obtained by polycondensation of phthalic anhydride and diethylene glycol and has a hydroxyl value of 315mgKOH/g.
5. The insulating material according to claim 3, characterized in that the following components are calculated in relative parts by mass: the using amount of the polyether polyol 1 is 1 to 2 parts by mass; the using amount of the polyether polyol 2 is 15 to 18 parts by mass; the using amount of the polyether polyol 3 is 18 to 20 parts by mass.
6. The thermal insulation material according to claim 1, wherein the mass ratio of trimethylolpropane to pentaerythritol is 3:1.
7. the insulation of claim 1, wherein the stabilizer is propylene carbonate, the blowing agent is pentafluoropropane, the flame retardant is triethyl phosphate, and the catalyst is one or more of N, N-dimethylcyclohexylamine, triethylenediamine, and bis (dimethylaminoethyl) ether.
8. A preparation method of the thermal insulation material as claimed in any one of claims 1 to 7, characterized in that the temperature of the isocyanate component and the isocyanate reactive component is controlled within 25 to 35 ℃, the isocyanate reactive component and the isocyanate reactive component are added into a high-pressure foaming machine and then injected into a mold, and the thermal insulation material is obtained after demolding and curing; wherein the pressure of a gun head of the high-pressure foaming machine is 135-145bar, and the temperature of a mould is controlled to be 40-45 ℃.
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