CN117986848A - Pultruded polyurethane door and window composite material and preparation method thereof - Google Patents
Pultruded polyurethane door and window composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 93
- 239000004814 polyurethane Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 35
- 239000004917 carbon fiber Substances 0.000 claims abstract description 35
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 22
- ZPDWRQORROQQLX-UHFFFAOYSA-N 4-[[2,4,4,6,6-pentakis(4-aminophenoxy)-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-trien-2-yl]oxy]aniline Chemical compound C1=CC(N)=CC=C1OP1(OC=2C=CC(N)=CC=2)=NP(OC=2C=CC(N)=CC=2)(OC=2C=CC(N)=CC=2)=NP(OC=2C=CC(N)=CC=2)(OC=2C=CC(N)=CC=2)=N1 ZPDWRQORROQQLX-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 15
- CUVVWDAHRRSSII-UHFFFAOYSA-N 4-bicyclo[4.2.0]octa-1(6),2,4,7-tetraenylmethanol Chemical compound OCC1=CC=C2C=CC2=C1 CUVVWDAHRRSSII-UHFFFAOYSA-N 0.000 claims abstract description 14
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical compound [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 56
- 230000008569 process Effects 0.000 claims description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
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- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 10
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- 239000000203 mixture Substances 0.000 claims description 5
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- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 3
- UYLSVYARXBFEKV-UHFFFAOYSA-N cyclobutane-1,3-diamine Chemical compound NC1CC(N)C1 UYLSVYARXBFEKV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- 230000009471 action Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
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- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of composite materials, in particular to a pultruded polyurethane door and window composite material and a preparation method thereof, wherein the composite material comprises an aluminum alloy and a polyurethane composite material, and the aluminum alloy is positioned on the outer surface of the polyurethane composite material; the polyurethane composite material comprises the following components in parts by mass: 70-85% of carbon fiber and 15-30% of polyurethane resin. According to the invention, the vinyl ester prepared from hexa (p-aminophenoxy) -cyclotriphosphazene, acryloyl chloride, 3- (2, 3) -glycidoxypropyl methyl dimethoxy silane, bisphenol A diglycidyl ether and 4-hydroxymethyl benzocyclobutene is added into the polyurethane composite material, so that the number of rigid functional groups and crosslinking sites in the polyurethane composite material system can be increased, the mechanical property and the water resistance of the door and window composite material are improved, and the interface combination at the interface of carbon fiber and polyurethane resin is improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a pultruded polyurethane door and window composite material and a preparation method thereof.
Background
Pultrusion refers to a process of implementing thermosetting, preset length cutting, continuous production and the like for fibers through dipping, pultrusion under external traction. Because of the unique stretching and extrusion molding process, the process has the advantages of high efficiency, low consumption, relatively high automation degree and the like. In practical use of the pultrusion process, resin materials may be used including: thermosetting epoxy resin, polyurethane, phenolic resin, thermoplastic polyethylene, polystyrene, polyacrylic acid, etc., and the fiber may be glass fiber, carbon fiber, basalt fiber, quartz fiber, etc. The product prepared by the pultrusion process can be used as a reinforcing section bar in the civil construction field instead of structural steel and alloy aluminum. However, some existing polyurethane door and window extruded profiles still have room for improvement in strength. Therefore, we propose a pultruded polyurethane door and window composite material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a pultruded polyurethane door and window composite material and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the pultruded polyurethane door and window composite material comprises an aluminum alloy and a polyurethane composite material, wherein the aluminum alloy is positioned on the outer surface of the polyurethane composite material;
The polyurethane composite material comprises the following components in parts by mass: 70-85% of carbon fiber and 15-30% of polyurethane resin.
Further, the polyurethane resin comprises the following components in parts by mass: 60 to 80 parts of polyether polyol, 80 to 100 parts of isocyanate, 20 to 40 parts of chain extender and 10 to 40 parts of vinyl ester.
Further, the polyether polyol is one of PTMG-1000, PTMG-2000, CP-56 and PPG.
Further, the isocyanate is one of Toluene Diisocyanate (TDI), 1, 5-Naphthalene Diisocyanate (NDI), hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI) and polymethylene polyphenyl polyisocyanate (PAPI).
Further, the vinyl ester is prepared by the following process:
Mixing hexa (p-aminophenoxy) -cyclotriphosphazene and triethylamine in N, N-dimethylformamide, regulating the temperature of the system to 0-5 ℃, slowly adding acryloyl chloride, reacting for 30-60 min, heating to 30-40 ℃, reacting for 90-120 min, heating to 60-70 ℃, and continuing to react for 8-12 h; vacuum distilling, washing and drying to obtain an acrylamide compound;
Mixing epoxy organic matter and N, N-dimethylformamide, adding 4-hydroxymethyl benzocyclobutene and potassium carbonate, and stirring for reacting for 60-90 min; adding an acrylamide compound, and reacting for 10-12 h at 100-120 ℃; vacuum distillation, washing and drying to obtain vinyl ester.
Further, the mol ratio of hexa (p-aminophenoxy) -cyclotriphosphazene, acryloyl chloride and triethylamine is 1 (6.0-6.5);
the ratio of hexa (p-aminophenoxy) -cyclotriphosphazene to N, N-dimethylformamide was 20g/100mL.
Further, the epoxy organic matter is the mixture of 3- (2, 3) -glycidoxypropyl methyl dimethoxy silane and bisphenol A diglycidyl ether, and the mass ratio is 1 (0.5-1.5);
The ratio of epoxy organic matter to N, N-dimethylformamide is 10g/100mL;
Further, the mass ratio of the epoxy organic matter, the 4-hydroxymethyl benzocyclobutene, the acrylamide compound and the potassium carbonate is (11.5-12.1): 1.2-1.4): 10 (0.06-0.10).
Further, the chain extender is one or more of 1, 3-cyclobutanediamine, tetramethylenediamine and 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
A preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
Mixing polyether polyol, a chain extender and vinyl ester to obtain a component A, and isocyanate to obtain a component B, namely a two-component glue solution (polyurethane resin);
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, and sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting to obtain a polyurethane composite material;
and adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, and curing to obtain the door and window composite material.
Further, the process conditions of the pultrusion process are as follows: the number of the tows of the carbon fiber is 12, and the pultrusion speed is 150-300 mm/min; in the extrusion molding and curing process, the material sequentially passes through a first die and a second die, wherein the temperature of the first die is 140-150 ℃, and the temperature of the second die is 190-210 ℃.
Further, after the pultrusion process, the composite material is subjected to post-treatment, wherein the post-treatment process comprises the following steps: the temperature is 130-135 ℃, and the heat preservation time is 210-270 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention discloses a pultrusion polyurethane door and window composite material, which is an organic polymer material obtained by polymerization reaction of diisocyanate monomer and polyol through polyurethane resin, and is characterized in that the functional group is carbamate. The polyol is polyether polyol, and ether bond contained in the polyol is not easy to hydrolyze, so that the polyurethane resin has better hydrolysis resistance, and the prepared polyurethane composite material has better water resistance. By adjusting the groups in the isocyanate and the polyol, it is helpful to adjust the rigid segment and the flexible segment of the polyurethane resin so that it has excellent toughness while maintaining high strength.
2. The invention discloses a pultruded polyurethane door and window composite material, which is added with vinyl ester. The acrylamide compound is prepared by the reaction of amino in hexa (p-aminophenoxy) -cyclotriphosphazene and acyl chloride in acryloyl chloride; the mixture of 3- (2, 3) -glycidoxypropyl methyl dimethoxy silane and bisphenol A diglycidyl ether is used as epoxy organic matter component, and the epoxy organic matter component is sequentially reacted with 4-hydroxymethyl benzocyclobutene and acrylamide compound to prepare vinyl ester with multi-vinyl functional groups. In the pultrusion process, the bi-component glue solution is polymerized in the system where the carbon fiber exists, and polyurethane resin is prepared by polyether polyol, isocyanate and chain extender. The polyunsaturated double bond structure in the vinyl ester can be added with amino groups in the prepared polyurethane resin, so that the number of rigid functional groups is increased, a three-dimensional network structure is formed, and crosslinking sites are increased, thereby being beneficial to improving the mechanical property, the thermal stability and the water resistance of the prepared polyurethane composite material. The benzocyclobutene structure exists in the vinyl ester system structure, ring opening occurs in the curing process, and a phthalene structure is formed between the benzocyclobutene and adjacent benzocyclobutene, so that the formation of a crosslinked network is promoted, the strength and the thermal stability of the prepared polyurethane composite material can be further improved, and the mechanical property and the water resistance of the door and window composite material are improved. The system also has a silicon-oxygen bond, so that the degradation of moisture at the interface of the carbon fiber and the polyurethane resin can be relieved while the crosslinking point is increased, and the interface combination at the interface of the carbon fiber and the polyurethane resin is improved.
3. According to the polyurethane door and window composite material formed by pultrusion, the polyurethane resin is continuously cured under the action of heat through post-treatment of the polyurethane composite material, and the post-curing is completed, so that the anisotropy of the polyurethane composite material formed by pultrusion can be relieved, the highly oriented molecular chains on the surface layer are relaxed, the residual stress is reduced, and the mechanical properties of the polyurethane composite material and the door and window composite material are improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following description of the embodiments of the present invention,
The carbon fiber is PAN-based carbon fiber (800 Tex), the fiber diameter is 7 mu m, the fiber density is 1.8g/cm < 3 >, the monofilament tensile strength is 3.75GPa, the monofilament tensile modulus is 210.2GPa, and the breaking elongation is 1.78%, and is from petrochemical company Limited on China petrochemical Shanghai;
Polyurethane adhesive: 8664 from Shenzhen Hancheng Dai Utility Co., ltd;
aluminum alloy: 6063, 0.2mm thick, from Hengtai aluminum Co., ltd;
the polyether polyol is PTMG-1000, and is obtained from Mitsubishi chemical corporation;
The "parts" described below are mass parts.
Example 1: a preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
Step 1, mixing 2.0g of hexa (p-aminophenoxy) -cyclotriphosphazene and triethylamine in 10mLN, N-dimethylformamide, regulating the temperature of the system to 5 ℃, slowly adding acryloyl chloride, reacting for 30min after adding in 30min, heating to 30 ℃, reacting for 120min, heating to 60 ℃, and continuing to react for 12h; vacuum distilling, washing and drying to obtain an acrylamide compound; the mole ratio of hexa (p-aminophenoxy) -cyclotriphosphazene, acryloyl chloride and triethylamine is 1:6.0:6.0;
Mixing 10g of epoxy organic matter and 100mLN, N-dimethylformamide, adding 4-hydroxymethyl benzocyclobutene and potassium carbonate, and stirring for reaction for 60min; adding an acrylamide compound, and reacting for 12 hours at 100 ℃; vacuum distilling, washing and drying to obtain vinyl ester; the epoxy organic matter is 3- (2, 3) -glycidoxypropyl methyl dimethoxy silane and bisphenol A diglycidyl ether, and the mass ratio is 1:1.5; the mass ratio of the epoxy organic matter to the 4-hydroxymethyl benzocyclobutene to the acrylamide compound to the potassium carbonate is 12.1:1.2:10:0.06;
step 2, mixing polyether polyol, chain extender tetramethylenediamine and vinyl ester to obtain a component A, and isocyanate to obtain a component B to obtain a bi-component glue solution;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting, then carrying out post-treatment, and preserving heat at 130 ℃ for 270min to obtain a polyurethane composite material; the process conditions of the pultrusion process are as follows: the tow number of the carbon fiber is 12, and the pultrusion speed is 300mm/min; the extrusion molding and curing process sequentially passes through a first die and a second die, wherein the first die is at 150 ℃ and the second die is at 210 ℃; the polyurethane composite material comprises 80wt% of carbon fiber and 20wt% of polyurethane resin; the two-component glue solution comprises 70 parts of polyether polyol, 80 parts of diphenylmethane diisocyanate, 30 parts of chain extender and 10 parts of vinyl ester;
And adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, standing for 24 hours, and curing to obtain the door and window composite material.
Example 2: a preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
Step 1, mixing 2.0g of hexa (p-aminophenoxy) -cyclotriphosphazene and triethylamine in 10mLN, N-dimethylformamide, regulating the temperature of the system to 2 ℃, slowly adding acryloyl chloride, reacting for 45min after 30min, heating to 35 ℃, reacting for 105min, heating to 65 ℃, and continuing to react for 10h; vacuum distilling, washing and drying to obtain an acrylamide compound; the mole ratio of hexa (p-aminophenoxy) -cyclotriphosphazene, acryloyl chloride and triethylamine is 1:6.2:6.3;
10g of epoxy organic matter and 100mLN, N-dimethylformamide are mixed, 4-hydroxymethyl benzocyclobutene and potassium carbonate are added, and the mixture is stirred and reacted for 75min; adding an acrylamide compound, and reacting for 11 hours at 110 ℃; vacuum distilling, washing and drying to obtain vinyl ester; the epoxy organic matter is 3- (2, 3) -glycidoxypropyl methyl dimethoxy silane and bisphenol A diglycidyl ether, and the mass ratio is 1:1; the mass ratio of the epoxy organic matter to the 4-hydroxymethyl benzocyclobutene to the acrylamide compound to the potassium carbonate is 11.8:1.3:10:0.08;
step 2, mixing polyether polyol, a chain extender 1, 3-cyclobutanediamine and vinyl ester to obtain a component A, and isocyanate to obtain a component B to obtain a bi-component glue solution;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting, then carrying out post-treatment, and preserving heat at 132 ℃ for 240min to obtain a polyurethane composite material; the process conditions of the pultrusion process are as follows: the tow number of the carbon fiber is 12, and the pultrusion speed is 25mm/min; the extrusion molding and curing process sequentially passes through a first die and a second die, wherein the temperature of the first die is 145 ℃, and the temperature of the second die is 200 ℃; the polyurethane composite material comprises 80wt% of carbon fiber and 20wt% of polyurethane resin; the two-component glue solution comprises 70 parts of polyether polyol, 83 parts of dicyclohexylmethane diisocyanate, 30 parts of chain extender and 25 parts of vinyl ester;
And adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, standing for 24 hours, and curing to obtain the door and window composite material.
Example 3: a preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
Step 1, mixing 2.0g of hexa (p-aminophenoxy) -cyclotriphosphazene and triethylamine in 10mLN, N-dimethylformamide, regulating the temperature of the system to 0 ℃, slowly adding acryloyl chloride, reacting for 60min after 30min, heating to 40 ℃ for 90min, heating to 70 ℃, and continuing to react for 8h; vacuum distilling, washing and drying to obtain an acrylamide compound; the mole ratio of hexa (p-aminophenoxy) -cyclotriphosphazene, acryloyl chloride and triethylamine is 1:6.5:6.5;
Mixing 10g of epoxy organic matter and 100mLN, N-dimethylformamide, adding 4-hydroxymethyl benzocyclobutene and potassium carbonate, and stirring for reaction for 90min; adding an acrylamide compound, and reacting for 10 hours at 120 ℃; vacuum distilling, washing and drying to obtain vinyl ester; the epoxy organic matter is 3- (2, 3) -glycidoxypropyl methyl dimethoxy silane and bisphenol A diglycidyl ether, and the mass ratio is 1:0.5; the mass ratio of the epoxy organic matter to the 4-hydroxymethyl benzocyclobutene to the acrylamide compound to the potassium carbonate is 11.5:1.2:10:0.06;
step 2, mixing polyether polyol, a chain extender 3,3 '-dichloro-4, 4' -diaminodiphenylmethane and vinyl ester to obtain a component A, and isocyanate to obtain a component B to obtain a bi-component glue solution;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting, then carrying out post-treatment, and preserving heat at 135 ℃ for 210min to obtain a polyurethane composite material; the process conditions of the pultrusion process are as follows: the tow number of the carbon fiber is 12, and the pultrusion speed is 150mm/min; the extrusion molding and curing process sequentially passes through a first die and a second die, wherein the temperature of the first die is 140 ℃, and the temperature of the second die is 190 ℃; the polyurethane composite material comprises 80wt% of carbon fiber and 20wt% of polyurethane resin; the two-component glue solution comprises 70 parts of polyether polyol, 80 parts of diphenylmethane diisocyanate, 30 parts of chain extender and 40 parts of vinyl ester;
And adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, standing for 24 hours, and curing to obtain the door and window composite material.
Comparative example 1: a preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
Step 1, mixing 2.0g of hexa (p-aminophenoxy) -cyclotriphosphazene and triethylamine in 10mLN, N-dimethylformamide, regulating the temperature of the system to 5 ℃, slowly adding acryloyl chloride, reacting for 30min after adding in 30min, heating to 30 ℃, reacting for 120min, heating to 60 ℃, and continuing to react for 12h; vacuum distilling, washing and drying to obtain an acrylamide compound; the mole ratio of hexa (p-aminophenoxy) -cyclotriphosphazene, acryloyl chloride and triethylamine is 1:6.0:6.0;
10g of bisphenol A diglycidyl ether and 100mLN, N-dimethylformamide are mixed, 4-hydroxymethyl benzocyclobutene and potassium carbonate are added, and the mixture is stirred and reacted for 60 minutes; adding an acrylamide compound, and reacting for 12 hours at 100 ℃; vacuum distilling, washing and drying to obtain vinyl ester; bisphenol A diglycidyl ether, 4-hydroxymethyl benzocyclobutene, acrylamide compound and potassium carbonate in a mass ratio of 14.1:1.2:10:0.06;
step 2, mixing polyether polyol, chain extender tetramethylenediamine and vinyl ester to obtain a component A, and isocyanate to obtain a component B to obtain a bi-component glue solution;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting, then carrying out post-treatment, and preserving heat at 130 ℃ for 270min to obtain a polyurethane composite material; the process conditions of the pultrusion process are as follows: the tow number of the carbon fiber is 12, and the pultrusion speed is 300mm/min; the extrusion molding and curing process sequentially passes through a first die and a second die, wherein the first die is at 150 ℃ and the second die is at 210 ℃; the polyurethane composite material comprises 80wt% of carbon fiber and 20wt% of polyurethane resin; the two-component glue solution comprises 70 parts of polyether polyol, 80 parts of diphenylmethane diisocyanate, 30 parts of chain extender and 10 parts of vinyl ester;
And adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, standing for 24 hours, and curing to obtain the door and window composite material.
Comparative example 2: a preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
Step 1, mixing 2.0g of 4,4' -biphenyldiamine and triethylamine in 10mLN, N-dimethylformamide, regulating the temperature of the system to 5 ℃, slowly adding acryloyl chloride, reacting for 30min after the addition is completed, heating to 30 ℃, reacting for 120min, heating to 60 ℃, and continuing to react for 12h; vacuum distilling, washing and drying to obtain an acrylamide compound; the molar ratio of the 4,4' -biphenyldiamine to the acryloyl chloride to the triethylamine is 1:6.0:6.0;
10g of bisphenol A diglycidyl ether and 100mLN, N-dimethylformamide are mixed, an acrylamide compound and potassium carbonate are added and reacted at 100 ℃ for 12 hours; vacuum distilling, washing and drying to obtain vinyl ester; bisphenol A diglycidyl ether, acrylamide compound and potassium carbonate in a mass ratio of 10.7:10:0.06;
step 2, mixing polyether polyol, chain extender tetramethylenediamine and vinyl ester to obtain a component A, and isocyanate to obtain a component B to obtain a bi-component glue solution;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting, then carrying out post-treatment, and preserving heat at 130 ℃ for 270min to obtain a polyurethane composite material; the process conditions of the pultrusion process are as follows: the tow number of the carbon fiber is 12, and the pultrusion speed is 300mm/min; the extrusion molding and curing process sequentially passes through a first die and a second die, wherein the first die is at 150 ℃ and the second die is at 210 ℃; the polyurethane composite material comprises 80wt% of carbon fiber and 20wt% of polyurethane resin; the two-component glue solution comprises 70 parts of polyether polyol, 80 parts of diphenylmethane diisocyanate, 30 parts of chain extender and 10 parts of vinyl ester;
And adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, standing for 24 hours, and curing to obtain the door and window composite material.
Comparative example 3: a preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
mixing polyether polyol, chain extender tetramethylenediamine and bisphenol A diallyl ether as a component A and isocyanate as a component B to obtain a bi-component glue solution;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting, then carrying out post-treatment, and preserving heat at 130 ℃ for 270min to obtain a polyurethane composite material; the process conditions of the pultrusion process are as follows: the tow number of the carbon fiber is 12, and the pultrusion speed is 300mm/min; the extrusion molding and curing process sequentially passes through a first die and a second die, wherein the first die is at 150 ℃ and the second die is at 210 ℃; the polyurethane composite material comprises 80wt% of carbon fiber and 20wt% of polyurethane resin; the two-component glue solution comprises 70 parts of polyether polyol, 80 parts of diphenylmethane diisocyanate, 30 parts of chain extender and 10 parts of bisphenol A diallyl ether;
And adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, standing for 24 hours, and curing to obtain the door and window composite material.
Comparative example 4: a preparation method of a pultruded polyurethane door and window composite material comprises the following preparation processes:
Mixing polyether polyol and chain extender tetramethylenediamine to obtain a component A and isocyanate to obtain a component B;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting, then carrying out post-treatment, and preserving heat at 130 ℃ for 270min to obtain a polyurethane composite material; the process conditions of the pultrusion process are as follows: the tow number of the carbon fiber is 12, and the pultrusion speed is 300mm/min; the extrusion molding and curing process sequentially passes through a first die and a second die, wherein the first die is at 150 ℃ and the second die is at 210 ℃; the polyurethane composite material comprises 80wt% of carbon fiber and 20wt% of polyurethane resin; the two-component glue solution comprises 70 parts of polyether polyol, 80 parts of diphenylmethane diisocyanate and 30 parts of chain extender;
And adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, standing for 24 hours, and curing to obtain the door and window composite material.
Experiment: taking the door and window composite materials and the polyurethane composite materials obtained in the examples 1-3 and the comparative examples 1-4, preparing samples, respectively detecting the performances of the samples and recording the detection results:
Mechanical property test: using GB/T1449 as a reference standard, adopting a three-point bending clamp to test the bending performance of the polyurethane composite material, wherein the sample size is 80mm multiplied by 15mm multiplied by 4mm, and the load rate is 2mm/min;
And (3) water resistance test: and (3) placing the polyurethane composite material in deionized water at 60 ℃ for soaking for 7d, taking out, drying at 40 ℃ for 24h, detecting the mechanical properties of the sample again, and taking the strength retention rate before and after the test as a performance index.
From the data in the above table, the following conclusions can be clearly drawn:
the polyurethane composites obtained in examples 1 to 3, in contrast to the polyurethane composites obtained in comparative examples 1 to 4, showed that the test results,
The polyurethane composites obtained in examples 1 to 3 have higher flexural strength in the transverse and longitudinal directions and higher retention of strength after hot water aging than the comparative examples. This fully demonstrates that the invention achieves improvements in strength and water resistance of the polyurethane composites, door and window composites produced.
In contrast to example 1, the vinyl ester of comparative example 1 was free of added component 3- (2, 3) -glycidoxypropyl methyldimethoxysilane; the vinyl ester of comparative example 2 was not added with the component 3- (2, 3) -glycidoxypropyl methyldimethoxysilane and replaced with hexa (p-aminophenoxy) -cyclotriphosphazene with 4,4' -biphenyldiamine; the vinyl ester of comparative example 3 was replaced with bisphenol a bis allyl ether; the polyurethane composite in comparative example 4 was not provided with the component vinyl ester. The polyurethane composites obtained in comparative examples 1 to 4 were reduced in flexural strength in the transverse and longitudinal directions and reduced in retention of strength after hot water aging. The invention can promote the improvement of the strength and the water resistance of polyurethane composite materials and door and window composite materials by adding the vinyl ester, the process and the arrangement of the components of the polyurethane composite materials.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: 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. A pultruded polyurethane door and window composite material is characterized in that: the aluminum alloy is adhered to the outer surface of the polyurethane composite material through a polyurethane adhesive;
The polyurethane composite material comprises the following components in parts by mass: 70-85% of carbon fiber and 15-30% of polyurethane resin.
2. A pultruded polyurethane door and window composite according to claim 1, wherein: the polyurethane resin comprises the following components in parts by mass: 60 to 80 parts of polyether polyol, 80 to 100 parts of isocyanate, 20 to 40 parts of chain extender and 10 to 40 parts of vinyl ester.
3. A pultruded polyurethane door and window composite according to claim 1, wherein: the vinyl ester is prepared by the following process:
mixing hexa (p-aminophenoxy) -cyclotriphosphazene and triethylamine in N, N-dimethylformamide, regulating the temperature of the system to 0-5 ℃, slowly adding acryloyl chloride, reacting for 30-60 min, heating to 30-40 ℃, reacting for 90-120 min, heating to 60-70 ℃, and continuing to react for 8-12 h to obtain an acrylamide compound;
Mixing epoxy organic matter and N, N-dimethylformamide, adding 4-hydroxymethyl benzocyclobutene and potassium carbonate, and stirring for reacting for 60-90 min; adding acrylamide compound, reacting at 100-120 deg.c for 10-12 hr to obtain vinyl ester.
4. A pultruded polyurethane door and window composite according to claim 3, wherein: the mol ratio of the hexa (p-aminophenoxy) -cyclotriphosphazene, the acryloyl chloride and the triethylamine is 1 (6.0-6.5) to 6.0-6.5.
5. A pultruded polyurethane door and window composite according to claim 3, wherein: the epoxy organic matter is the mixture of 3- (2, 3) -glycidoxypropyl methyl dimethoxy silane and bisphenol A diglycidyl ether, and the mass ratio is 1 (0.5-1.5).
6. A pultruded polyurethane door and window composite according to claim 3, wherein: the mass ratio of the epoxy organic matter to the 4-hydroxymethyl benzocyclobutene to the acrylamide compound to the potassium carbonate is (11.5-12.1): 1.2-1.4): 10 (0.06-0.10).
7. The pultruded polyurethane door and window composite according to claim 6, wherein: the chain extender is one or more of 1, 3-cyclobutanediamine, tetramethylenediamine and 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
8. A preparation method of a pultruded polyurethane door and window composite material is characterized by comprising the following steps of: the preparation method comprises the following preparation processes:
Mixing polyether polyol, a chain extender and vinyl ester to obtain a component A, and isocyanate to obtain a component B to obtain a bi-component glue solution;
Mounting carbon fibers on a creel, spreading yarns, adopting a pultrusion process, and sequentially carrying out fiber arrangement, injection dipping of bi-component glue solution, preforming, extrusion molding, solidification, cooling and cutting to obtain a polyurethane composite material;
and adhering the aluminum alloy to the outer surface of the polyurethane composite material through the polyurethane adhesive, and curing to obtain the door and window composite material.
9. The method for preparing the pultruded polyurethane door and window composite material according to claim 8, which is characterized in that: the process conditions of the pultrusion process are as follows: the number of the tows of the carbon fiber is 12, and the pultrusion speed is 150-300 mm/min; in the extrusion molding and curing process, the material sequentially passes through a first die and a second die, wherein the temperature of the first die is 140-150 ℃, and the temperature of the second die is 190-210 ℃.
10. The method for preparing the pultruded polyurethane door and window composite material according to claim 8, which is characterized in that: after the pultrusion process, the composite material is subjected to post-treatment, wherein the post-treatment process comprises the following steps: the temperature is 130-135 ℃, and the heat preservation time is 210-270 min.
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