CN115746245B - Transparent polyurethane composite material and preparation method and application thereof - Google Patents
Transparent polyurethane composite material and preparation method and application thereof Download PDFInfo
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- CN115746245B CN115746245B CN202211491752.3A CN202211491752A CN115746245B CN 115746245 B CN115746245 B CN 115746245B CN 202211491752 A CN202211491752 A CN 202211491752A CN 115746245 B CN115746245 B CN 115746245B
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 49
- 239000004814 polyurethane Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 11
- 239000006260 foam Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004970 Chain extender Substances 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 51
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 27
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 14
- 239000001361 adipic acid Substances 0.000 claims description 13
- 235000011037 adipic acid Nutrition 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- -1 lauryldiacid Chemical compound 0.000 claims description 7
- 229960004063 propylene glycol Drugs 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 235000013772 propylene glycol Nutrition 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 3
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940117969 neopentyl glycol Drugs 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 229940113165 trimethylolpropane Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002780 morpholines Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940100573 methylpropanediol Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a transparent polyurethane composite material and a preparation method and application thereof, wherein the polyurethane composite material comprises a component A and a component B, raw materials of the component A comprise polyester polyol a, a chain extender, a cross-linking agent, a foam stabilizer and a catalyst, and raw materials of the component B comprise the following components: the polyester polyol b is prepared by polymerization reaction of straight-chain small molecular alcohol, branched-chain small molecular alcohol and aliphatic polybasic acid, wherein the mass of the branched-chain small molecular alcohol accounts for 40-72% of the total mass of the straight-chain small molecular alcohol and the branched-chain small molecular alcohol. According to the invention, the specific polyester polyol is selected in the component B, and the side chain groups in the polyester polyol are utilized to disturb the ordered arrangement of the macromolecular polyurethane structure, so that the macromolecular polyurethane structure is disordered, the transparency of a product prepared from the transparent polyurethane composite material is greatly improved, and the transparent polyurethane composite material has no shrinkage, good appearance and strong tensile force.
Description
Technical Field
The invention particularly relates to a transparent polyurethane composite material and a preparation method and application thereof.
Background
Polyurethane is a generic name of macromolecular compounds containing repeating urethane groups in the main chain, and is a macromolecular polymer obtained by the interaction of a dibasic or polybasic organic isocyanate with a polyol compound.
At present, polyurethane materials can be divided into foaming type materials and non-foaming type materials, wherein the non-foaming type materials belong to injection molding materials and can be used for manufacturing transparent soles, but the transparency is often not ideal, the weight is large, the cost is high, and the application range of the polyurethane materials is greatly limited. And the foam material has lower transparency.
In addition, the sole of polyurethane materials has good comfort, particularly in terms of shock absorption and noise reduction, but due to its low transparency, it is difficult to meet the increasing demands of people for the appearance and sensory comfort of polyurethane materials, and in order to obtain polyurethane materials with good transparency, the strength properties of polyurethane materials are often impaired.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide the transparent polyurethane composite material with high strength and high transparency, and the transparent polyurethane composite material also has the advantage of short mold opening time, so that the production efficiency is greatly improved.
A second object of the present invention is to provide a transparent article prepared using the transparent composition.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The transparent polyurethane composite material comprises a component A and a component B, wherein the raw materials of the component A comprise the following components in parts by weight:
the raw materials of the component B comprise the following components in parts by weight:
35-45 parts of polyester polyol b;
55-65 parts of isocyanate;
the polyester polyol b is prepared by polymerization reaction of straight-chain small molecular alcohol, branched-chain small molecular alcohol and aliphatic polybasic acid, wherein the mass of the branched-chain small molecular alcohol accounts for 40-72% of the total mass of the straight-chain small molecular alcohol and the branched-chain small molecular alcohol.
According to some embodiments of the invention, the linear small molecule alcohol is one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol.
According to some embodiments of the invention, the branched small molecule alcohol is one or more of ethyl butyl propylene glycol, 2, 4-trimethyl 1, 3-pentanediol, 1, 3-butanediol, methyl propylene glycol, neopentyl glycol, 1, 2-propanediol, trimethylolpropane; and/or the aliphatic polybasic acid is one or a combination of a plurality of adipic acid, succinic acid, sebacic acid, lauryldiacid, 1, 4-cyclohexane dicarboxylic acid and azelaic acid.
According to some embodiments of the invention, the polyester polyol b has a functionality of 2 to 2.1 and a hydroxyl number of 35 to 85mg KOH/g. Preferably, the polyester polyol b has a functionality of 2 to 2.1 and a hydroxyl number of 40 to 60mg KOH/g.
Further, the polymerization reaction for preparing the polyester polyol b is carried out in the presence of a catalyst which is one or a combination of one of titanate, organotin compound, bismuth compound, amine substance, morpholine derivative of an organic ligand or a complex ligand.
Further, the preparation method of the polyester polyol b comprises the following steps: adding linear chain micromolecule alcohol, branched chain micromolecule alcohol and aliphatic polybasic acid into a reaction kettle, heating to 150-170 ℃, carrying out esterification reaction, controlling the water outlet rate and the tower top temperature to 98-102 ℃, heating to 230-240 ℃ at the heating rate of 10-15 ℃/h, adding a catalyst to keep the temperature for 0.5-1.5 h when the water outlet amount reaches more than 95% of the theoretical water outlet amount, and vacuumizing to obtain the polyester polyol b with the acid value lower than 1mgKOH/g and the hydroxyl value of 35-85 mgKOH/g.
The vacuumizing adopts a method of gradually reducing the vacuum degree, and the vacuum degree is finally controlled to be less than 0.096MPa.
According to some embodiments of the invention, the isocyanate is a combination of 4, 4-diphenylmethane diisocyanate and carbodiimide-modified MDI, wherein the mass of the carbodiimide-modified MDI is 10 to 15% of the total mass of the isocyanate. For example, the isocyanate is selected from MDI-100 (Wanhua chemical group Co., ltd.), wannate1631 (Wanhua liquefied MDI), MM103C (German Basiff Co., ltd.).
According to some embodiments of the invention, the polyester polyol a has a functionality of 2 and a hydroxyl number of 45 to 94mg KOH/g.
Further, the polyester polyol a is prepared by polymerization reaction of polybasic acid and polyhydric alcohol, wherein the polybasic acid is one or more of adipic acid, succinic acid, sebacic acid, lauryldiacid, 1, 4-cyclohexanedicarboxylic acid and azelaic acid, and the polyhydric alcohol is one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, ethylbutylpropanediol, 2, 4-trimethyl 1, 3-pentanediol, 1, 3-butanediol, methylpropanediol, 1, 6-hexanediol, neopentyl glycol, 1, 2-propanediol and trimethylolpropane.
Further, the polymerization reaction for preparing the polyester polyol a is carried out in the presence of a catalyst which is one or a combination of one of titanate, organotin compound, bismuth compound, amine substance and morpholine derivative of an organic ligand or a complex ligand.
Further, the preparation method of the polyester polyol a comprises the following steps: adding polyalcohol and polybasic acid into a reaction kettle, heating to 150-170 ℃, carrying out esterification reaction, controlling the water outlet rate and the tower top temperature to 98-102 ℃, heating to 230-240 ℃ at the heating rate of 10-15 ℃/h, adding a catalyst to keep the temperature for 0.5-1.5 h when the water outlet amount reaches more than 95% of the theoretical water outlet amount, and vacuumizing to obtain the polyester polyol a with the acid value lower than 1mgKOH/g and the hydroxyl value of 45-94 mgKOH/g.
According to some embodiments of the invention, the chain extender is one or a combination of several of 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol.
According to some embodiments of the invention, the cross-linking agent is one or a combination of several of glycerol, trimethylolpropane, diethanolamine, and triethanolamine.
According to some embodiments of the invention, the component B further comprises 20 to 40ppm of a polymerization inhibitor, wherein the polymerization inhibitor is phosphoric acid. The polymerization inhibitor is used for inhibiting side reactions and preventing intermolecular polymerization and crosslinking from forming netlike macromolecules.
According to some embodiments of the invention, the catalyst in the a-component is one or a combination of several of dibutyltin dilaurate, triethylenediamine, bis (dimethylaminoethyl) ether, a delayed catalyst. For example, one or a mixture of several of dibutyltin dilaurate (T-12), triethylenediamine (A-33) or a delay catalyst Dabco 1027 (America air chemical products Co., ltd.).
According to some embodiments of the invention, the foam stabilizer is a silicone surfactant. For example, one or two of the foam homogenizing agents DC-193 and DC-3041 of America air chemical products limited are selected. DC-3041 has low freezing point, does not freeze, and can improve fluidity. DC-193 can improve surface appearance while maintaining excellent dimensional stability.
The transparent polyurethane composite material of the invention does not contain foaming agent.
According to some embodiments of the invention, the mass ratio of the A component to the B component is 100:40-80.
The second technical scheme adopted by the invention is as follows: the preparation method of the transparent polyurethane composite material comprises the following steps:
(1) Preparation of component A
Mixing polyester polyol a, a chain extender, a cross-linking agent, a foam stabilizer and a catalyst to obtain a component A;
(2) Preparation of component B
Adding the polyester polyol B, isocyanate or/and polymerization inhibitor into a reaction kettle, reacting at 70-80 ℃ until the mass content of NCO is 18-23%, and ending the reaction to obtain the component B.
The invention adopts a third technical scheme that: the transparent product comprises a transparent part, wherein the transparent part is made of the transparent polyurethane composite material, and the transparent product comprises a transparent sole and a motor vehicle shock absorption block.
The preparation method comprises the steps of adding the component A and the component B into a low-pressure sole machine, vacuumizing to remove bubbles, pouring the component A and the component B into a mold, curing and molding, and opening the mold for 1.5-2.5 min to obtain the transparent sole.
The hardness of the transparent sole is 45-85A, no bubbles or flaws exist on the surface, the transparency is good, and the glossiness and the performance are excellent.
The temperature of the die is 40-50 ℃ and the temperature of the material is 35-45 ℃.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the polyurethane composite material consists of the component A with a specific formula and the component B with a specific formula, and meanwhile, the specific polyester polyol is selected to be used for the component B, and the side chain groups in the polyester polyol are utilized to disorder the ordered arrangement of the macromolecular polyurethane structure, so that the macromolecular polyurethane structure is disordered, the transparency of a product prepared from the transparent polyurethane composite material is greatly improved, the transparent polyurethane composite material is free from shrinkage, has good appearance and can bear stronger tensile force.
The transparent polyurethane composite material provided by the invention has the advantages that the surface friction coefficient is increased due to the existence of the side methyl in the polyurethane molecular structure, and the transparent polyurethane composite material is a non-foaming material and has a larger contact area, so that the transparent polyurethane composite material can be used for manufacturing an anti-skid transparent material.
The transparent polyurethane composite material can meet the mold opening requirement of 2-3 min, has almost zero defective rate, effectively improves the production efficiency, has stable product quality and is easy to prepare.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples, but the practice and protection scope of the present invention is not limited thereto.
All the raw materials used in the following examples and comparative examples are commercially available, except for the specific descriptions.
Example 1
This example provides a polyester polyol a1, which is prepared by the following method:
in nitrogen atmosphere, 156.8kg of ethylene glycol, 227.5kg of 1.4-butanediol and 615.7kg of adipic acid are added into a reaction kettle, the temperature is raised to 150-170 ℃, water is generated, the water outlet speed is controlled, the temperature of the tower top is ensured to be 98-102 ℃, and the temperature is kept constant for 1h and then the temperature is continuously raised; continuously reacting at 160-230 ℃ for 3 hours, discharging water, adding 20g of catalyst, continuously heating to react, heating to 240 ℃ for 1 hour, and dealcoholizing for 2.5 hours by adopting a method of gradually reducing the vacuum degree under the vacuum state to obtain the polyester polyol a1 with the functionality of 2, the hydroxyl value of 76.3mgKOH/g and the acid value of 0.3 mgKOH/g.
Example 2
This example provides a polyester polyol a2, which is prepared by the following method:
In nitrogen atmosphere, adding 244.6kg of diethylene glycol, 153.3kg of ethylene glycol and 602.1kg of adipic acid into a reaction kettle, heating to 150-170 ℃, starting to generate water, controlling the water outlet speed, ensuring the temperature of the tower top to be 98-102 ℃, keeping the constant temperature for 1h, and then continuing to heat; continuing to react at 160-230 ℃ for 3h, finishing water yielding, adding 30g of catalyst, continuing to heat up to react, heating to 240 ℃ for 1h, adopting a method of gradually reducing the vacuum degree in a vacuum state, and dealcoholizing for 3.5h to obtain the polyester polyol a2 with the functionality of 2, the hydroxyl value of 45.2mgKOH/g and the acid value of 0.2 mgKOH/g.
Example 3
This example provides a polyester polyol a3, which is prepared by the following method:
In nitrogen atmosphere, 126.2kg of ethylene glycol, 201.5kg of 1.4 butanediol, 77.4kg of 1.2 propanediol and 594.9kg of adipic acid are added into a reaction kettle, the temperature is raised to 150-170 ℃, water is generated, the water outlet speed is controlled, the tower top temperature is ensured to be 98-102 ℃, and the temperature is kept constant for 1h and then the temperature is continuously raised; continuing to react at 160-230 ℃ for 3h, finishing water yielding, adding 25g of catalyst, continuing to heat up to react, heating to 240 ℃ for 1h, adopting a method of gradually reducing the vacuum degree in a vacuum state, and dealcoholizing for 2.5h to obtain the polyester polyol a3 with the functionality of 2, the hydroxyl value of 90.1mgKOH/g and the acid value of 0.4 mgKOH/g.
Example 4
This example provides a polyester polyol b1, which is prepared by the following method:
In nitrogen atmosphere, adding 99.4kg of ethylene glycol, 127.4kg of diethylene glycol, 187.7kg of neopentyl glycol and 585.5kg of adipic acid into a reaction kettle, heating to 150-170 ℃, starting to have water, controlling the water outlet speed, ensuring the temperature of the tower top to be 98-102 ℃, keeping the constant temperature for 1h, and then continuously heating; continuing to react at 160-230 ℃ for 3h, finishing water yielding, adding 40g of catalyst, continuing to heat up to react, heating to 240 ℃ for 1h, adopting a method of gradually reducing the vacuum degree in a vacuum state, and dealcoholizing for 3.5h to obtain the polyester polyol b1 with the functionality of 2, the hydroxyl value of 37.0mgKOH/g and the acid value of 0.3 mgKOH/g.
Example 5
This example provides a polyester polyol b2, which is prepared by the following method:
preparing polyester b2, namely adding 125.8kg of ethylene glycol, 126.4kg of 1, 2-propylene glycol, 109.5kg of 1, 3-butanediol, 474.2kg of adipic acid and 164.1kg of sebacic acid into a reaction kettle in a nitrogen atmosphere, heating to 150-170 ℃, starting water generation, controlling the water outlet speed, ensuring the temperature of the top of the tower to be 98-102 ℃, keeping the temperature for 1h, and then continuously heating; continuing to react at 160-230 ℃ for 3h, finishing water yielding, adding 25g of catalyst, continuing to heat up to react, heating to 240 ℃ for 1h, adopting a method of gradually reducing the vacuum degree in a vacuum state, and dealcoholizing for 2.5h to obtain the polyester polyol b2 with the functionality of 2, the hydroxyl value of 76.2mgKOH/g and the acid value of 0.4 mgKOH/g.
Example 6
This example provides a polyester polyol b3, which is prepared by the following method:
Preparing polyester b3, namely adding 124.9kg of ethylene glycol, 266.4kg of neopentyl glycol, 54kg of trimethylolpropane, 412.1kg of adipic acid and 142.6kg of succinic acid into a reaction kettle in a nitrogen atmosphere, heating to 150-170 ℃, starting water generation, controlling the water outlet speed, ensuring the temperature of the top of the tower to be 98-102 ℃, keeping the temperature for 1h, and then continuously heating; and (3) continuing the reaction at 160-230 ℃ for 3h, finishing water yielding, adding 35g of catalyst, continuing the heating reaction, raising the temperature to 240 ℃ for 1h, adopting a method of gradually reducing the vacuum degree in a vacuum state, and dealcoholizing for 2.5h to obtain the polyester polyol b3 with the functionality of 2.08, the hydroxyl value of 56.2mgKOH/g and the acid value of 0.5 mgKOH/g.
Example 7
The embodiment provides a transparent polyurethane composite material, which consists of a component A and a component B, wherein:
The component A is prepared by the following method: 100kg of polyester polyol a1, 3.5kg of ethylene glycol, 2kg of 1, 4-butanediol, 1kg of glycerol, 500g of foam homogenizing agent DC3041, 1.8kg of catalyst A33 and 0.2kg of catalyst Dabco 1027 are mixed, heated to 55 ℃, stirred for 2 hours, cooled to 45 ℃ and discharged, and the mixture is sealed and stored to obtain a component A.
The component B is prepared by the following method: adding 520kg of 4, 4-diphenylmethane diisocyanate into a reaction kettle, keeping the temperature at 50 ℃, adding 30g of phosphoric acid, stirring for 15min, then adding 422kg of polyester polyol B1, controlling the process temperature to be not more than 70 ℃, heating to 75 ℃ after the temperature is stable, reacting for 2h, adding 58kg of liquefied MDI, stirring for 0.5h, sampling and detecting, cooling to 45 ℃ for discharging, and sealing and preserving to obtain the component B.
When the product is manufactured, the mass ratio of the component A to the component B is 100:71.
Example 8
The embodiment provides a transparent polyurethane composite material, which consists of a component A and a component B, wherein:
The component A is prepared by the following method: 100kg of polyester polyol a2, 1.5kg of ethylene glycol, 1kg of 1, 2-propylene glycol, 1kg of triethanolamine, 500g of foam stabilizer DC-193, 2kg of catalyst A33 and 0.2kg of catalyst Dabco 1027 are respectively weighed and added into a reaction kettle, the temperature is raised to 55 ℃, the mixture is stirred for 2 hours, the mixture is cooled to below 45 ℃ and discharged, and the mixture is hermetically stored to obtain a component A.
The component B is prepared by the following method: weighing 570kg of 4, 4-diphenylmethane diisocyanate, adding into a reaction kettle, keeping the temperature at 50 ℃, adding 25g of phosphoric acid, stirring for 15min, then adding 380kg of polyester polyol B2, controlling the process temperature to be not more than 70 ℃, heating to 73 ℃ after the temperature is stable, reacting for 2h, adding 50kg of liquefied MDI, stirring for 0.5h, sampling and detecting, cooling to 42 ℃ for discharging, and sealing and preserving to obtain the component B.
When the product is manufactured, the mass ratio of the component A to the component B is 100:41.
Example 9
The embodiment provides a transparent polyurethane composite material, which consists of a component A and a component B, wherein:
The component A is prepared by the following method: 100kg of polyester polyol A3, 5kg of 1, 4-butanediol, 1kg of trimethylolpropane, 600g of foam stabilizer DC-193 and 1.7kg of catalyst A33 are respectively weighed, added into a reaction kettle, heated to 55 ℃, stirred for 2 hours, cooled to below 43 ℃ and discharged, and the mixture is sealed and preserved to obtain the component A.
The component B is prepared by the following method: 560kg of 4, 4-diphenylmethane diisocyanate is weighed, added into a reaction kettle, the temperature is kept at 50 ℃,40 g of phosphoric acid is added, stirring is carried out for 15min, then 360kg of polyester polyol B3 is added, the temperature is controlled to be not more than 70 ℃, the temperature is stabilized, the temperature is raised to 76 ℃, the reaction is carried out for 2h, 80kg of liquefied MDI is added, stirring is carried out for 0.5h, the sampling detection is carried out, the mass content of NCO is 19.7%, the temperature is reduced to 41 ℃, the material is discharged, and the material is sealed and preserved, thus the component B is obtained.
When the product is manufactured, the mass ratio of the component A to the component B is 100:68.
Comparative example 1
The polyurethane composition provided in this comparative example is composed of a component a and a component B, wherein the a component and the B component are substantially the same as in example 7, except that: in the B component, a commercially available polyester polyol CMA-244 having a number average molecular weight of 3000 was used in place of the polyester polyol B1.
In this example, polyester polyol CMA-244 is a commercially available product from Huada chemical group, inc., and is prepared by polymerizing adipic acid, ethylene glycol, and 1, 4-butanediol.
Comparative example 2
The polyurethane composition provided in this comparative example is composed of a component A and a component B, wherein the component A and the component B are substantially the same as in example 8, and differ from example 8 in that: in the B component, a commercially available polyester polyol MX-706 having a number average molecular weight of 1500 was used in place of the polyester polyol B2.
In this example, polyester polyol MX-706 is a commercially available product from Huada chemical group, inc., which is prepared by polymerizing adipic acid, ethylene glycol, diethylene glycol.
Comparative example 3
The polyurethane composition provided in this comparative example is composed of a component a and a component B, wherein the a component and the B component are substantially the same as in example 7, except that:
the polyester polyol B1 in the component B is replaced by a polyester polyol prepared by the following method:
In nitrogen atmosphere, adding 99.5kg of ethylene glycol, 316kg of neopentyl glycol and 584.5kg of adipic acid into a reaction kettle, heating to 150-170 ℃, starting water generation, controlling the water outlet speed, ensuring the temperature of the tower top to be 98-102 ℃, keeping the temperature for 1h, and then continuously heating; continuously reacting at 160-230 ℃ for 3h, finishing water yielding, adding 40g of catalyst, continuously heating to 240 ℃ for 1h, gradually reducing the vacuum degree in a vacuum state, and dealcoholizing for 3.5h to obtain the polyester polyol with the functionality of 2, the hydroxyl value of 37.0mgKOH/g and the acid value of 0.3 mgKOH/g.
Comparative example 4
The polyurethane composition provided in this comparative example is composed of a component a and a component B, wherein the a component and the B component are substantially the same as in example 7, except that: the component A is not added with the cross-linking agent glycerol.
The polyurethane compositions prepared in examples 7 to 9 and comparative examples 1 to 4 were cast to prepare soles according to the following casting method: and respectively placing the component A and the component B in a low-pressure sole machine, preheating, vacuumizing to remove bubbles, respectively pouring the component A and the component B into an aluminum alloy mold, curing and molding, and opening the mold for 2min to obtain the sole product.
The performance of the sole articles prepared using the polyurethane compositions of examples 7 to 9 and comparative examples 1 to 4 was tested and the results are shown in Table 1.
Table 1 shows the results of performance tests on sole articles prepared with the polyurethane compositions of examples 7 to 9 and comparative examples 1 to 4
In table 1: the hardness test standard is according to the Shore A hardness standard of rubber.
The appearance of the article was tested by visual inspection to observe the transparency and surface condition of the article.
The method for testing the shrinkage condition of the product comprises the following steps: testing the size change condition, observing the size change condition of a test piece with the length of 200mm, and after 24 hours, if the size of the test piece is within the range of 200+/-0.5 mm, determining that the test piece is not shrunk (namely, the size change of the test piece is not more than 0.5 mm); if the size of the test piece is changed to be 0.5-1 mm, the test piece slightly contracts; if the size of the test piece is changed to be 1-2 mm, the test piece is slightly lengthened; if the test piece size is changed to 2mm or more, the test piece is deformed.
Tensile strength and elongation are in accordance with GB/528-2009 standard.
The polyurethane compositions of the representative examples 7-9 of the invention are used for preparing sole products, which have good appearance, good transparency, quick shaping and no defective products.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (6)
1. A transparent polyurethane composite material consists of a component A and a component B, and is characterized in that,
The raw materials of the component A comprise the following components in parts by weight:
100 parts of polyester polyol a;
1-6 parts of a chain extender;
0.5-2 parts of cross-linking agent;
0.4-0.8 parts of foam stabilizer;
1.0-2.5 parts of a catalyst;
the raw materials of the component B comprise the following components in parts by weight:
35-45 parts of polyester polyol b;
55-65 parts of isocyanate;
The polyester polyol b is prepared by carrying out polymerization reaction on straight-chain small-molecule alcohol, branched-chain small-molecule alcohol and aliphatic polybasic acid, wherein the mass of the branched-chain small-molecule alcohol accounts for 40-72% of the total mass of the straight-chain small-molecule alcohol and the branched-chain small-molecule alcohol;
The straight-chain small molecular alcohol is one or a combination of more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol and 1, 6-hexanediol;
the branched small molecular alcohol is one or a combination of more of ethyl butyl propylene glycol, 2, 4-trimethyl-1, 3-pentanediol, 1, 3-butanediol, methyl propylene glycol, neopentyl glycol, 1, 2-propanediol and trimethylolpropane;
The aliphatic polybasic acid is one or a combination of a plurality of adipic acid, succinic acid, sebacic acid, lauryldiacid, 1, 4-cyclohexanedicarboxylic acid and azelaic acid;
the mass ratio of the component A to the component B is 100:40-80;
The polyester polyol a is prepared by polymerization reaction of polybasic acid and polyhydric alcohol, wherein the polybasic acid is one or a combination of more of adipic acid, succinic acid, sebacic acid, lauryldiacid, 1, 4-cyclohexanedicarboxylic acid and azelaic acid, and the polyhydric alcohol is one or a combination of more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol and 1, 6-hexanediol;
The cross-linking agent is one or a combination of a plurality of glycerol, trimethylolpropane, diethanolamine or triethanolamine;
The isocyanate is a combination of 4, 4-diphenylmethane diisocyanate and carbodiimide modified MDI, wherein the mass of the carbodiimide modified MDI accounts for 10-15% of the total mass of the isocyanate.
2. The transparent polyurethane composite according to claim 1, wherein: the functionality of the polyester polyol b is 2-2.1, and the hydroxyl value is 35-85 mg KOH/g.
3. The transparent polyurethane composite according to claim 1, wherein: the functionality of the polyester polyol a is 2, and the hydroxyl value is 45-94 mg KOH/g.
4. The transparent polyurethane composite according to claim 1, wherein: the chain extender is one or the combination of more of 1, 4-butanediol, ethylene glycol, propylene glycol and diethylene glycol; and/or the component B also contains 20-40 ppm of polymerization inhibitor; and/or, the foam stabilizer is an organosilicon surfactant.
5. A method for preparing the transparent polyurethane composite material according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
(1) Preparation of component A
Mixing polyester polyol a, a chain extender, a cross-linking agent, a foam stabilizer and a catalyst to obtain a component A;
(2) Preparation of component B
And adding the polyester polyol B and isocyanate into a reaction kettle, reacting at 70-80 ℃ until the mass content of NCO is 18-23%, and ending the reaction to obtain the component B.
6. A transparent article comprising a transparent portion, characterized in that: the transparent part is made of the transparent polyurethane composite material according to any one of claims 1-4, and the transparent product comprises a transparent sole and a motor vehicle shock absorption block.
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