CN116970142A - Transparent low-hardness impact-resistant polyurethane elastomer and preparation method thereof - Google Patents
Transparent low-hardness impact-resistant polyurethane elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN116970142A CN116970142A CN202311225715.2A CN202311225715A CN116970142A CN 116970142 A CN116970142 A CN 116970142A CN 202311225715 A CN202311225715 A CN 202311225715A CN 116970142 A CN116970142 A CN 116970142A
- Authority
- CN
- China
- Prior art keywords
- component
- dimer acid
- polyurethane elastomer
- preparation
- resistant polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 35
- 239000000539 dimer Substances 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 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 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 25
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 2
- 210000003127 knee Anatomy 0.000 description 2
- 230000004630 mental health Effects 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008451 emotion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 210000000707 wrist Anatomy 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4812—Mixtures of polyetherdiols with 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a transparent low-hardness impact-resistant polyurethane elastomer and a preparation method thereof. The preparation method comprises the following steps of (1) preparation of the component A: mixing a chain extender, dimer acid modified dimer acid polyester polyol and polyether polyol, dehydrating until the water content is less than 0.05%, cooling, adding an antioxidant and a catalyst, and stirring to obtain a component A; (2) preparation of a component B: heating dimer acid modified dimer acid polyester polyol, polyether polyol and diisocyanate to react to obtain a prepolymer B component; (3) And mixing the component A and the component B, pouring into a mold, demolding, and vulcanizing and placing at normal temperature to obtain the transparent low-hardness impact-resistant polyurethane elastomer. According to the preparation method provided by the invention, the appearance of the product system is transparent by adding the specific dimer acid polyester polyol, and meanwhile, the system crystallinity is reduced by mixing and blending the polyester and the polyether polyol, so that the effect of absorbing impact force of the product system is achieved.
Description
Technical Field
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a transparent low-hardness impact-resistant polyurethane elastomer and a preparation method thereof.
Background
Nowadays, along with the improvement of attention of people to the physical and mental health of the people, more and more people improve the physical and mental health level of the people through exercises, such as riding, skidding and the like, the exercises have interestingness, meanwhile, the muscles of the body can be efficiently exercised, and negative emotion can be released in the riding and skidding processes. However, riding, skidding and other exercises have certain dangers, especially knees and palms, and people need to protect the body of the people when the people exercise, so that the exercise protective clothing can play a role in buffering impact force in the exercise process, and the acting force of the joint palms is reduced, so that the effect of protecting the human body is achieved.
Polyurethane protective products in the current market are products with higher hardness, such as helmets, goggles and the like, and achieve the protection purpose by avoiding the direct contact between a human body and an impact object; the foam type products, such as sports knee pads, wrist pads, gloves and the like, play a role in protecting human bodies through foaming and buffering stress, and tend to have lower hardness and poorer strength.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the transparent low-hardness impact-resistant polyurethane elastomer which is used for manufacturing glove protective equipment and has the characteristics of colorless and transparent appearance, low hardness, high performance, excellent impact resistance effect, no foaming of a system, excellent operation performance and environmental protection.
The invention also provides a preparation method, which is simple and feasible and can realize industrial production.
The transparent low-hardness impact-resistant polyurethane elastomer is prepared by mixing a component A and a component B;
the component A is prepared from the following raw materials in percentage by mass:
4-6% of a chain extender;
30-40% of dimer acid modified dimer acid polyester polyol;
polyether polyol 1.2-65.4%;
0.3-1% of an antioxidant;
0.3-0.8% of a catalyst;
the component B is prepared from the following raw materials in percentage by mass:
22.2-32.5% of dimer acid modified dimer acid polyester polyol;
polyether polyol 2.5-11.9%;
59.4-68.3% of diisocyanate;
the component B is a prepolymer with the isocyanate group mass content of 18-22 percent
The polyether polyol 1 has a number average molecular weight of 3200g/mol and a functionality of 3;
the polyether polyol 2 has a number average molecular weight of 400g/mol and a functionality of 2.
The dimer acid modified dimer acid polyester polyol has the number average molecular weight of 1000 and the functionality of 2, and is obtained by adding dimer acid for esterification and transesterification.
The preparation method of the dimer acid modified dimer acid polyester polyol comprises the following steps: adding dimer fatty acid, succinic acid and 1, 4-butanediol into production equipment, adding a catalyst, starting stirring, heating and heating, protecting the reaction equipment by nitrogen, controlling the heating rate to be 15-25 ℃/h, heating and discharging water, heating to 190-210 ℃ and preserving heat for 2-2.5 h, starting vacuum and heating to 220-230 ℃ and preserving heat for 3-3.5 h; and (5) detecting the acid value, equivalent weight and water content, and cooling to 140-150 ℃ for discharging for standby.
The catalyst is tetrabutyl titanate.
The charging mass ratio of the dimer fatty acid, the succinic acid and the 1, 4-butanediol is preferably 1:1.1:2.
The chain extender is an alcohol chain extender, the number average molecular weight is 45-134, and one or more of BDO, DPG and diethylene glycol are preferred.
The mixing mass ratio of the component A to the component B is 100 (35-55).
The diisocyanate is one or two of MDI-50, diphenylmethane diisocyanate, isophorone diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
The antioxidant is one or more of UV-531, UV-02, UV-01, 1010 or 1076.
The catalyst is a heat sensitive catalyst, preferably NTCAT SA102, purchased from New typical chemical materials Inc.
The preparation method of the transparent low-hardness impact-resistant polyurethane elastomer comprises the following steps:
(1) And (3) preparation of the component A: mixing a chain extender, dimer acid modified dimer acid polyester polyol, polyether polyol 1 and polyether polyol 2, dehydrating at 100-110 ℃ under the vacuum pressure of 0.09-0.095 MPa until the water content is less than 0.05%, cooling to 50-60 ℃, adding an antioxidant and a catalyst, and stirring to obtain a component A;
(2) And (3) preparation of a component B: the dimer acid modified dimer acid polyester polyol, polyether polyol and diisocyanate with the water content controlled below 0.05% are reacted for 3-12 hours at the temperature of 80-100 ℃ to obtain a prepolymer B component with the isocyanate content of 18-22%;
(3) And mixing the component A and the component B according to the mass ratio, pouring into a mold, demolding for 5-8 min, and vulcanizing and placing at normal temperature to obtain the transparent low-hardness impact-resistant polyurethane elastomer.
The temperature of the mixing in the step (3) is 40-60 ℃, and the temperature of the die is 60-70 ℃.
And (3) vulcanizing and placing for 10-16 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is a casting type elastomer, the system is not foamed, and the shock resistance is excellent.
(2) The transparent low-hardness impact-resistant polyurethane elastomer prepared by the invention is applied to sports glove protective equipment, has the hardness below 50A, the tensile strength above 6MPa, the elongation above 500 percent and the mechanical property and the wear resistance superior to those of foaming products.
(3) According to the preparation method provided by the invention, the appearance of the product system is transparent by adding the specific dimer acid polyester polyol, and meanwhile, the system crystallinity is reduced by mixing and blending the polyester and the polyether polyol, so that the effect of absorbing impact force of the product system is achieved.
Detailed Description
The present invention will be further illustrated by the following examples, wherein the raw materials used in the examples are commercially available conventional raw materials unless otherwise specified.
The following examples, without specific description, refer to the percentages by mass.
The raw materials described in the examples, which are not specifically described, are all commercially available.
The materials used in the examples are as follows:
EP-330N, number average molecular weight 3200g/mol, functionality 3, blue Star Dong Dachemical responsibility Co., ltd;
INOV C204, number average molecular weight 400g/mol, functionality 2, new material Co., ltd;
pure MDI: diphenylmethane diisocyanate, wanhua chemical group Co., ltd;
MDI-50: mixtures of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, wanhua chemical group Co., ltd;
antioxidant 1076: antioxidants, basf, germany;
catalyst NTCAT SA102, heat-sensitive catalyst, new classical chemical materials Co., ltd;
diethylene glycol: chain extender, number average molecular weight 106, satellite chemicals limited.
Preparation of dimer acid modified dimer acid polyester polyol PE-8010:
adding dimer fatty acid, succinic acid and 1, 4-butanediol into production equipment, wherein the mass ratio is 1:1.1:2, adding tetrabutyl titanate serving as a catalyst, starting stirring, heating and heating, protecting nitrogen of reaction equipment, controlling the heating rate to be 20+/-5 ℃/h, heating and discharging water, heating to 200+/-10 ℃, preserving heat for 2h, starting vacuum, heating to 225+/-5 ℃, and continuously preserving heat for 3h; detecting that the acid value is less than 0.06mgKOH/g, the hydroxyl value is 112.2mgKOH/g, the water content is less than 0.05%, cooling to 145+/-5 ℃ after being qualified, and discharging for standby. PE-8010: number average molecular weight 1000, functionality 2.
Example 1
The preparation method of the transparent low-hardness impact-resistant polyurethane elastomer comprises the following steps:
(1) And (3) preparation of the component A: 4% of diethylene glycol, 30% of PE-8010 and 65.4% of EP-330N are dehydrated to water content of less than 0.05% at 105+/-5 ℃ and minus 0.095MPa, then cooled to 55+/-5 ℃, and then 0.3% of antioxidant 1076,0.3% of NTCAT SA102 is added, and the mixture is fully and uniformly stirred to obtain the component A.
(2) And (3) preparation of a component B: 22.2% PE-8010, 9.5% INOV C204, 48.3% pure MDI,20% MDI-50, and reacted at 90+ -10deg.C for 3 hours to obtain a prepolymer B having isocyanate content of 22%.
(3) Mixing A, B components according to the weight ratio of 100:35, uniformly mixing at the temperature of 50+/-5 ℃, rapidly pouring into a mold at the temperature of 65+/-5 ℃, demolding for 8min, and vulcanizing at normal temperature for 10h to obtain the polyurethane elastomer.
Example 2
The preparation method of the transparent low-hardness impact-resistant polyurethane elastomer comprises the following steps:
(1) And (3) preparation of the component A: 4% of diethylene glycol, 30% of PE-8010 and 65.4% of EP-330N, dehydrating until the water content is less than 0.05% below 105+/-5 ℃ and-0.095 MPa, cooling to 55+/-5 ℃, adding 0.3% of antioxidant 1076,0.3% of NTCAT SA102, and fully and uniformly stirring to obtain the component A.
(2) And (3) preparation of a component B: 27.8% PE-8010, 11.9% INOV C204, 40.3% pure MDI,20% MDI-50 were reacted at 90+ -10deg.C for 3h to give a prepolymer B having an isocyanate content of 18%.
(3) Mixing A, B components according to the weight ratio of 100:42, uniformly mixing at the temperature of 50+/-5 ℃, rapidly pouring into a mold at the temperature of 65+/-5 ℃, demolding for 8min, and vulcanizing at normal temperature for 13h to obtain the polyurethane elastomer.
Example 3
The preparation method of the transparent low-hardness impact-resistant polyurethane elastomer comprises the following steps:
(1) And (3) preparation of the component A: 6% of diethylene glycol, 40% of PE-8010 and 52.2% of EP-330N, dehydrating until the water content is less than 0.05% below 105+/-5 ℃ and-0.095 MPa, cooling to 55+/-5 ℃, adding 1% of antioxidant 1076,0.8% of NTCAT SA102, and fully and uniformly stirring to obtain the component A.
(2) And (3) preparation of a component B: 26% PE-8010, 6.5% INOV C204 and 67.5% pure MDI were reacted at 90.+ -. 10 ℃ for 3 hours to give a prepolymer having an isocyanate content of 22%.
(3) Mixing A, B components according to the weight ratio of 100:45, uniformly mixing at the temperature of 50+/-5 ℃, rapidly pouring into a mold at the temperature of 65+/-5 ℃, demolding for 8min, and vulcanizing at normal temperature for 13h to obtain the polyurethane elastomer.
Example 4
The preparation method of the transparent low-hardness impact-resistant polyurethane elastomer comprises the following steps:
(1) And (3) preparation of the component A: 6% of diethylene glycol, 40% of PE-8010 and 52.2% of EP-330N, dehydrating below 105+/-5 ℃ and-0.095 MPa until the water content is less than 0.05%, cooling to 55+/-5 ℃, adding 1% of antioxidant 1076,0.8% of NTCAT SA102, and fully and uniformly stirring to obtain the component A.
(2) And (3) preparation of a component B: 32.5% PE-8010, 8.1% INOV C204, 59.4% pure MDI, and reacted at 90+ -10deg.C for 3h to obtain a prepolymer B having an isocyanate content of 18%.
(3) Mixing A, B components according to the weight ratio of 100:55, uniformly mixing at the temperature of 50+/-5 ℃, rapidly pouring into a mold at the temperature of 65+/-5 ℃, demolding for 8min, vulcanizing at normal temperature for 16h, and obtaining the polyurethane elastomer.
Example 5
The preparation method of the transparent low-hardness impact-resistant polyurethane elastomer comprises the following steps:
(1) And (3) preparation of the component A:
and (3) a component A: 5% of diethylene glycol, 35% of PE-8010 and 59% of EP-330N, dehydrating below 105+/-5 ℃ and-0.095 MPa until the water content is less than 0.05%, cooling to 55+/-5 ℃, adding 0.5% of antioxidant 1076,0.5% of NTCAT SA102, and fully and uniformly stirring to obtain the component A.
(2) And (3) preparation of a component B: 28.6% PE-8010, 9.5% INOV C204, 61.9% pure MDI, at 90+ -10deg.C for 3h to obtain prepolymer with isocyanate content of 19%.
(3) Mixing A, B components according to the weight ratio of 100:42, uniformly mixing at the temperature of 50+/-5 ℃, rapidly pouring into a mold at the temperature of 65+/-5 ℃, demolding for 8min, and vulcanizing at normal temperature for 16h to obtain the polyurethane elastomer.
Comparative example 1
The polyurethane foam protector product with the model JYL-z1906 manufactured by Qingdao Jinlai New Material Co., ltd was manufactured into test pieces with the same thickness for testing.
Comparative example 2
The PE-8010 polyester polyol of example 1 was replaced with a commercially available product from Qingdao Xinyutian chemical Co., ltd: polyester polyol POL-3112, number average molecular weight 1000, functionality 2.
(1) And (3) preparation of the component A: 4% of diethylene glycol, 30% of POL-3112 and 59.4% of EP-330N are dehydrated to water content of less than 0.05% below 105+/-5 ℃ and-0.095 MPa, then cooled to 55+/-5 ℃, and 0.3% of antioxidant 1076,0.3% of NTCAT SA102 is added, and the component A is obtained after full and uniform stirring.
(2) And (3) preparation of a component B: 22.2% POL-3112, 9.5% INOV C204, 48.3% pure MDI,20% MDI-50 were reacted at 90.+ -. 10 ℃ for 3 hours to give a prepolymer B having an isocyanate content of 22%.
(3) Mixing A, B components according to the weight ratio of 100:35, uniformly mixing at the temperature of 50+/-5 ℃, rapidly pouring into a mold at the temperature of 65+/-5 ℃, demolding for 8min, and vulcanizing at normal temperature for 10h to obtain the polyurethane elastomer.
Comparative example 3
Polyurethane elastomers were prepared and tested by replacing the polyether polyol in the A component of example 1 with polyester polyol PE-8010.
(1) And (3) preparation of the component A: 4% of diethylene glycol and 95.4% of PE-8010 are dehydrated to water content less than 0.05% at 105+/-5 ℃ and minus 0.095MPa, then cooled to 55+/-5 ℃,0.3% of antioxidant 1076,0.3% of NTCAT SA102 is added, and the mixture is fully and uniformly stirred to obtain the component A.
(2) And (3) preparation of a component B: 22.2% PE-8010, 9.5% INOV C204, 48.3% pure MDI,20% MDI-50, and reacted at 90+ -10deg.C for 3 hours to obtain a prepolymer B having isocyanate content of 22%.
(3) Mixing A, B components according to the weight ratio of 100:37, uniformly mixing at the temperature of 50+/-5 ℃, rapidly pouring into a mold at the temperature of 65+/-5 ℃, demolding for 8min, and vulcanizing at normal temperature for 10h to obtain the polyurethane elastomer.
Test pieces prepared in the comparative examples above were tested according to the following criteria:
hardness is measured according to GB/T531.1-2008 standard;
tensile strength was measured according to GB/T528-2009 standard;
impact resistance is measured according to ANSI 138-2019 standard;
TABLE 1 impact resistance Classification Table
TABLE 2 Performance test of test pieces prepared in examples and comparative examples
The data show that the impact resistance grade of the polyurethane foam can completely reach the level of the polyurethane foam, and the mechanical property of the polyurethane foam is far higher than that of the polyurethane foam; after the common polyester polyol is replaced, the product cannot be colorless and transparent due to the property that the polyester polyol and the polyether polyol are not mutually soluble; after the polyether polyol is removed, the impact resistance level of the system is reduced due to higher crystallinity of the system.
Claims (9)
1. A transparent low-hardness impact-resistant polyurethane elastomer is characterized by being prepared by mixing a component A and a component B according to the mass ratio of 100 (35-55);
the component A is prepared from the following raw materials in percentage by mass:
4-6% of a chain extender;
30-40% of dimer acid modified dimer acid polyester polyol;
polyether polyol 1.2-65.4%;
0.3-1% of an antioxidant;
0.3-0.8% of a catalyst;
the component B is prepared from the following raw materials in percentage by mass:
22.2-32.5% of dimer acid modified dimer acid polyester polyol;
polyether polyol 2.5-11.9%;
59.4-68.3% of diisocyanate;
the polyether polyol 1 has a number average molecular weight of 3200g/mol and a functionality of 3;
the polyether polyol 2 has a number average molecular weight of 400g/mol and a functionality of 2.
2. The transparent low hardness impact resistant polyurethane elastomer of claim 1, wherein said dimer acid modified dimer acid polyester polyol has a number average molecular weight of 1000 and a functionality of 2.
3. The transparent low-hardness impact-resistant polyurethane elastomer according to claim 2, wherein the dimer acid-modified dimer acid polyester polyol is prepared by the following steps: adding dimer fatty acid, succinic acid and 1, 4-butanediol into production equipment, adding a catalyst, starting stirring, heating and heating, protecting the reaction equipment by nitrogen, controlling the heating rate to 15-25 ℃/h, heating and discharging water, heating to 190-210 ℃, preserving heat, starting vacuum and heating to 220-230 ℃ for continuous heat preservation; and cooling to 140-150 ℃ after the material is qualified, and discharging for standby.
4. A transparent low hardness impact resistant polyurethane elastomer according to claim 3, wherein the catalyst used in the preparation of said dimer acid modified dimer acid polyester polyol is tetrabutyl titanate.
5. The transparent low hardness impact resistant polyurethane elastomer of claim 1, wherein the catalyst is a heat sensitive catalyst.
6. The transparent low hardness impact resistant polyurethane elastomer according to claim 1, wherein said diisocyanate is one or two of MDI-50, diphenylmethane diisocyanate, isophorone diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
7. A method for preparing the transparent low-hardness impact-resistant polyurethane elastomer according to any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) And (3) preparation of the component A: mixing a chain extender, dimer acid modified dimer acid polyester polyol and polyether polyol 1, dehydrating at 100-110 ℃ under the vacuum pressure of 0.09-0.095 MPa until the water content is less than 0.05%, cooling to 50-60 ℃, adding an antioxidant and a catalyst, and stirring to obtain a component A;
(2) And (3) preparation of a component B: the dimer acid modified dimer acid polyester polyol, polyether polyol 2 and diisocyanate with the water content controlled below 0.05% are reacted at 80-100 ℃ to obtain a component B;
(3) And mixing the component A and the component B, pouring into a mold, demolding, and vulcanizing and placing at normal temperature to obtain the transparent low-hardness impact-resistant polyurethane elastomer.
8. The method for preparing a transparent low-hardness impact-resistant polyurethane elastomer according to claim 7, wherein the temperature of the mixing in the step (3) is 40-60 ℃, and the temperature of the mold is 60-70 ℃.
9. The method for preparing a transparent low-hardness impact-resistant polyurethane elastomer according to claim 7, wherein the vulcanizing and placing time in the step (3) is 10-16 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311225715.2A CN116970142B (en) | 2023-09-22 | 2023-09-22 | Transparent low-hardness impact-resistant polyurethane elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311225715.2A CN116970142B (en) | 2023-09-22 | 2023-09-22 | Transparent low-hardness impact-resistant polyurethane elastomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116970142A true CN116970142A (en) | 2023-10-31 |
| CN116970142B CN116970142B (en) | 2024-01-05 |
Family
ID=88477047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311225715.2A Active CN116970142B (en) | 2023-09-22 | 2023-09-22 | Transparent low-hardness impact-resistant polyurethane elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116970142B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015137316A (en) * | 2014-01-23 | 2015-07-30 | 東ソー株式会社 | Polyurethane elastomer-forming composition for elastic member for roll, and elastic member for roll using the composition |
| CN114316196A (en) * | 2021-12-29 | 2022-04-12 | 上海华峰新材料研发科技有限公司 | Hydrolysis-resistant polyurethane damping material and preparation method and application thereof |
| CN116102709A (en) * | 2023-02-23 | 2023-05-12 | 旭川化学（苏州）有限公司 | Polyurethane composite material for filling solid core of tire and preparation method and application thereof |
| CN116284666A (en) * | 2023-04-07 | 2023-06-23 | 广东盛天体育股份有限公司 | Wear-resistant polyurethane micro-foaming runway material and preparation method thereof |
-
2023
- 2023-09-22 CN CN202311225715.2A patent/CN116970142B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015137316A (en) * | 2014-01-23 | 2015-07-30 | 東ソー株式会社 | Polyurethane elastomer-forming composition for elastic member for roll, and elastic member for roll using the composition |
| CN114316196A (en) * | 2021-12-29 | 2022-04-12 | 上海华峰新材料研发科技有限公司 | Hydrolysis-resistant polyurethane damping material and preparation method and application thereof |
| CN116102709A (en) * | 2023-02-23 | 2023-05-12 | 旭川化学（苏州）有限公司 | Polyurethane composite material for filling solid core of tire and preparation method and application thereof |
| CN116284666A (en) * | 2023-04-07 | 2023-06-23 | 广东盛天体育股份有限公司 | Wear-resistant polyurethane micro-foaming runway material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116970142B (en) | 2024-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2482436C (en) | Polyurethane elastomers from hdi prepolymers with reduced content of free hdi monomers | |
| KR100507007B1 (en) | Thermoplastic polyether urethane | |
| US4786703A (en) | Process for the preparation of polyisocyanate prepolymers and polyurethanes having high temperature performance and low hysteresis | |
| AU2008200020B2 (en) | Polyurethanes cured with amines and their preparation | |
| KR102205059B1 (en) | Manufacturing method of polyurethane resin, polyurethane resin and molded product | |
| WO2014186111A2 (en) | Thermoplastic polyurethane from low free monomer prepolymer | |
| KR20190041018A (en) | Thermoplastic polyurethane resin for foaming, method for producing the same, and molded article | |
| JPH04502780A (en) | thermoplastic polyurethane | |
| CN104448197B (en) | The synthetic method of the Heat-resistant Polyurethane Elastomers | |
| CN112824435A (en) | High-regularity thermoplastic polyurethane material and preparation method thereof | |
| CN112574385B (en) | Anti-slippery low-rolling-resistance thermoplastic polyurethane elastomer and preparation method thereof | |
| CN116970142B (en) | Transparent low-hardness impact-resistant polyurethane elastomer and preparation method thereof | |
| CN103865251A (en) | Thermoplastic polyurethane elastomer injection molding composition and injection molding product thereof | |
| EP2235086B1 (en) | Low melting polyurethane elastomers | |
| CN102040722B (en) | Preparation method of high-performance polyurethane elastomer | |
| US3014894A (en) | Polyurethane plastics | |
| EP3808532A1 (en) | Recycling of cast polyurethane | |
| CN112679694A (en) | Preparation method of high-performance polyurethane elastomer | |
| CN114316189A (en) | Impact-resistant protective thermoplastic polyurethane material and preparation method thereof | |
| CN112538149B (en) | Preparation process of casting polyurethane elastomer | |
| EP1950234A1 (en) | Polyurethanes cured with amines and their preparation | |
| CN110573548B (en) | Process for preparing polyurethanes using polyester polyols comprising polycyclic aromatic moieties | |
| CN116355168A (en) | Low-temperature-resistant buffer high polymer material formula | |
| CN116874714B (en) | Polyurethane foaming tyre with low hysteresis loss and preparation method thereof | |
| JPS61303A (en) | Shoe sole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |