CN111518306A - Cell opening agent, thermoplastic polyurethane foam and preparation method thereof - Google Patents
Cell opening agent, thermoplastic polyurethane foam and preparation method thereof Download PDFInfo
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- CN111518306A CN111518306A CN202010391176.XA CN202010391176A CN111518306A CN 111518306 A CN111518306 A CN 111518306A CN 202010391176 A CN202010391176 A CN 202010391176A CN 111518306 A CN111518306 A CN 111518306A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emergency Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a pore-opening agent, which consists of at least one alkynediol polyoxyalkylene ether alcohol, phthalic acid ester, organosilicon surfactant and dimethyl silicone oil. The invention also provides a preparation method of the pore forming agent. The invention also provides thermoplastic polyurethane foam which is composed of the composite polyether, the cell opening agent and isocyanate. The invention also provides a preparation method of the thermoplastic polyurethane foam. The prepared thermoplastic polyurethane foam is cut into slices, and the slices are subjected to cold-pressing forming at the temperature of 140-160 ℃ to prepare the roof interior trim which is used for automobiles and has the functions of sound absorption, noise reduction and heat insulation. The invention adopts the novel cell opening agent for preparing the thermoplastic polyurethane foam, improves the operation latitude of the process, improves the cell opening rate of the foam and improves the sound absorption effect of the foam.
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to a polyurethane material, in particular to a cell opener, thermoplastic polyurethane foam and a preparation method thereof.
Background
With the development of the Chinese automobile industry, the China automobile output and sales volume continuously stays at the top of the world for many years, consumers pay more and more attention to the comfort in the automobile driving process, the noise of the automobile is always the main factor of the comfort, 80% of sound insulation materials adopted in the current market are thermoplastic polyurethane foam, and the thermoplastic polyurethane foam has the functions of heat insulation and buffer protection.
The thermoplastic polyurethane foam is a porous material, the pores are communicated with each other to form continuous cavities, and the opening rate of the thermoplastic polyurethane foam is required to reach more than 90 percent. Thermoplastic polyurethane foams are generally prepared by reacting a polyether polyol and/or polyester polyol, water, a catalyst, a silicone surfactant, a cell opener, a small amount of a physical blowing agent, and the like, with an isocyanate. The addition amount of the cell opener in the composite polyether is about 0.5%, and although the addition amount is small, the cell opener plays a role in opening cells at the foam molding later stage, and is very important for preparing thermoplastic polyurethane foam.
Most of the pore formers used in the market are O-501 products of special chemical companies, which are created in consideration of product confidentiality, and all the products are produced in Germany factories; therefore, the selling price of O-501 to China is more than 120 Yuan. At present, O-501 is monopolized in the market, and the invention develops a cell opening agent for thermoplastic polyurethane foam to fill the domestic blank.
Disclosure of Invention
The invention aims to provide a cell opening agent, thermoplastic polyurethane foam and a preparation method thereof, and the cell opening agent, the thermoplastic polyurethane foam and the preparation method thereof aim to solve the technical problem that the thermoplastic polyurethane foam in the prior art is poor in heat insulation and buffer protection effects
The invention provides a pore forming agent, which consists of the following components in percentage by mass:
further, the general formula of the alkynediol polyoxyalkylene ether alcohol is as follows:
H(C2H4O)b(C3H6O)aO(R1)(R2)C≡C(R3)(R4)O(C3H6O)a(C2H4O)bh, wherein R1、R3Is methyl or ethyl; r2、R4Is selected from C3～C9Alkyl groups of (a); a is a numerical value of 3-6 and represents the mole number of the propylene oxide group in the polyoxyethylene ether; b is a numerical value of 6-10 and represents the mole number of ethylene oxide groups in the polyoxyethylene ether.
Further, the phthalate ester is diisononyl phthalate or dioctyl phthalate.
Furthermore, the organic silicon surfactant is a nonionic surfactant with high ethylene oxide content, the molecular weight is 4000-6000 g/mol, and the content of the polysiloxane-polyalkylene oxide copolymer is 30-60 wt%.
Further, the viscosity of the dimethyl silicone oil is 10-350 mPa.s.
The invention also provides a preparation method of the pore forming agent, which comprises the following steps:
the first step is as follows: firstly, mixing one or more alkynediol polyoxyalkylene ether alcohols, an organic silicon surfactant and dimethyl silicone oil according to a mass ratio, pumping the mixture into an emulsifying kettle in vacuum, replacing air in the reaction kettle by nitrogen, keeping the system at normal pressure and at the temperature of 55-65 ℃, stirring for 1-2 hours, cooling to 30-40 ℃ to obtain an alkynediol/organic silicon emulsion,
the second step is that: mixing the alkynediol/organic silicon emulsion obtained in the first step and phthalic acid ester according to a mass ratio, pumping the mixture into a stirring kettle in vacuum, replacing air in the reaction kettle by nitrogen, maintaining the system at normal pressure, and stirring the mixture for 0.5 to 2 hours at normal temperature to obtain the pore-forming agent.
The invention also provides thermoplastic polyurethane foam which is prepared from the following components in parts by weight:
the viscosity of the combined polyether is 300-700 mPa.s, the hydroxyl value is 100-200 mgKOH/g, and the mass percentage of water is 6.0-7.0%.
Preferably, the weight ratio of the pore former to the polyol is 0.5: 100.
the polyester polyol is phthalic anhydride polyester polyol, the viscosity is 2000-10000 mPa.s, the hydroxyl value is 200-400 mgKOH/g, and the acid ester is less than or equal to 2.0 mgKOH/g.
The organosilicon surfactant is polysiloxane-polyoxyalkylene copolymer, and can be selected from S series products of Shanghai Maihao chemical technology, Inc., B series products of winning group, L series products of Mi-Tuo high-new material, AK series products of Jiangsu Meiside chemical industry, Inc., preferably S-3219 of Shanghai Maihao chemical technology, Inc.
Specifically, the isocyanate is polyphenyl polymethylene polyisocyanate (polymeric MDI), and is selected from any one or more of PM200, PM2010, PM400, M20S and 44V20, preferably PM 200; the preferred ratio is 140 parts per 100 parts polyol.
The invention also provides a preparation method of the thermoplastic polyurethane foam, which comprises the steps of weighing and combining polyether polyol, polyester polyol, an organosilicon surfactant and a cell opening agent according to the mass ratio, and fully mixing to prepare a composition; then the composition and isocyanate are fully mixed according to the proportion and poured into a special mould for reaction and foaming to prepare the thermoplastic polyurethane foam.
The prepared foam is cut into slices, and the slices are subjected to cold-pressing forming at the temperature of 140-160 ℃ to prepare the roof interior trim which is used for automobiles and has the functions of sound absorption, noise reduction and heat insulation.
Compared with the prior art, the invention has positive and obvious effect. The invention adopts the novel cell opening agent for preparing the thermoplastic polyurethane foam, improves the operation latitude of the process, improves the cell opening rate of the foam and improves the sound absorption effect of the foam.
The present invention is further illustrated by the following examples.
Detailed Description
Example 1
400g of alkynediol polyoxyalkylene ether alcohol which is started from 1, 4-butynediol (the mole number is 1) and has the mole number of 3 of ethylene oxide and the mole number of 6 of propylene oxide are added into a 2000ml four-neck flask with a fixing device, a constant temperature function, mechanical stirring, a thermocouple, a vacuum device and nitrogen gas introduction, 100g of an organic silicon surfactant and 50g of simethicone with the viscosity of 350mPa.s are sequentially added, stirring is started at normal temperature under the protection of nitrogen gas, the stirring temperature is 60 ℃, and stirring is carried out for 1 hour. This product is referred to herein as an acetylenic diol/silicone emulsion.
550g of the above-mentioned acetylene glycol/silicone emulsion and 400g of diisononyl phthalate were added in succession to a 2000ml four-neck flask equipped with a fixing device, a thermostatic function, mechanical stirring, a thermocouple, a vacuum device and nitrogen gas introduction, and stirring was started under nitrogen protection at normal temperature at 23 ℃ for 0.5 hour. Cell opener example 1 was prepared.
Example 2
In a 2000ml four-neck flask with a fixing device, a constant temperature function, mechanical stirring, a thermocouple, a vacuum device and nitrogen gas introduction, 800g of 3-methyl-1-dodecyn-3-ol (the mole number is 1) starting alkynediol polyoxyalkylene ether alcohol with the mole number of ethylene oxide of 6 and the mole number of propylene oxide of 10 is added, 70 g of organic silicon surfactant and 30 g of dimethyl silicone oil with the viscosity of 10mPa.s are sequentially added, stirring is started at normal temperature under the protection of nitrogen gas, the stirring temperature is 60 ℃, and stirring is started for 1 hour. This product is referred to herein as an acetylenic diol/silicone emulsion.
900g of the acetylene glycol/silicone emulsion and 100g of dioctyl phthalate are sequentially added into a 2000ml four-neck flask with a fixing device, a constant temperature function, mechanical stirring, a thermocouple, a vacuum device and nitrogen, stirring is started under the protection of nitrogen, and stirring is carried out at normal temperature at 23 ℃ for 0.5 hour. Cell opener example 2 was prepared.
Example 3 preparation of thermoplastic polyurethane foam:
thermoplastic polyurethane foams were prepared using the above examples 1, 2, and the foam formulations and foam property test results are shown in table 1 below:
the temperature of the composition prepared by mixing polyether polyol, polyester polyol, organosilicon surfactant and cell opener with a 2-component high-pressure foaming machine and isocyanate is controlled to be 20 +/-1 ℃, the mixing pressure of a gun head of a high-pressure machine is regulated to be 120-150kPa, the material discharge amount of the gun head of the high-pressure machine is 4 kg/second, and the component metering precision deviation of the high-pressure machine is 2%. After the raw materials were thoroughly mixed by a machine tip, thermoplastic polyurethane foam was prepared in an open mold with a length, width and height of 2000, 1600, 1000mm, the mold temperature was controlled at 45 ± 2 ℃.
After the foam was aged for 48 hours at 23 + -2 deg.C, the foam was tested for various properties. Meanwhile, the foam without open cells is selected as a comparative example 1, the foam with the pioneering special chemical cell opening agent O-501 is selected as a comparative example 2, and the test results are shown in Table 1.
TABLE 1 comparison of Properties of thermoplastic polyurethane foams
A combination polyether polyol (DmcBlock 2001) from shanghai merck technologies ltd, hydroxyl value 150mgKOH/g, viscosity 500 mpa.s;
the polyester polyol (PS-3152) is from Spiral (Nanjing) chemical Co., Ltd, has a hydroxyl value of 315mgKOH/g and a viscosity of 2200 mPa.s;
the organosilicon surfactant (S-3219) is from Shanghai Maihao New Material science and technology, Inc.;
polyphenyl polymethylene polyisocyanate (PM200) from nicotineaux corporation, viscosity 200mpa.s, NCO content 31%;
o-501 was from pioneering specialty Chemicals (Shanghai) Inc.
The data in Table 1 show that examples 1, 2 of the present invention have good cell openability and process adaptability for application to thermoplastic polyurethane foams, as compared to the comparative example without the cell opener; the prepared foam has good dimensional stability and toughness.
Claims (9)
1. The pore forming agent is characterized by comprising the following components in percentage by mass:
the general formula of the alkynediol polyoxyalkylene ether alcohol is as follows:
H(C2H4O)b(C3H6O)aO(R1)(R2)C≡C(R3)(R4)O(C3H6O)a(C2H4O)bh, wherein R1、R3Is methyl or ethyl; r2、R4Is selected from C3～C9Alkyl groups of (a); a is a numerical value of 3-6 and represents the mole number of the propylene oxide group in the polyoxyethylene ether; b is a numerical value of 6-10 and represents the mole number of ethylene oxide groups in the polyoxyethylene ether.
2. The cell opener of claim 1, wherein: the phthalate is diisononyl phthalate or dioctyl phthalate.
3. The cell opener of claim 1, wherein: the organic silicon surfactant is a nonionic surfactant with high ethylene oxide content, the molecular weight is 4000-6000 g/mol, and the content of the polysiloxane-polyalkylene oxide copolymer is 30-60 wt%.
4. The cell opener of claim 1, wherein: the viscosity of the dimethyl silicone oil is 10-350 mPa.s.
5. The method of claim 1, comprising the steps of:
the first step is as follows: mixing one or more alkynediol polyoxyalkylene ether alcohols, an organic silicon surfactant and dimethyl silicone oil according to a mass ratio, vacuumizing into an emulsifying kettle, replacing air in the reaction kettle by nitrogen, keeping the system at normal pressure and at the temperature of 55-65 ℃, stirring for 1-2 hours, and cooling to 30-40 ℃ to obtain an alkynediol/organic silicon emulsion;
the second step is that: mixing the alkynediol/organic silicon emulsion obtained in the first step and phthalic acid ester according to a mass ratio, pumping the mixture into a stirring kettle in vacuum, replacing air in the reaction kettle by nitrogen, maintaining the system at normal pressure, and stirring the mixture for 0.5 to 2 hours at normal temperature to obtain the pore-forming agent.
6. The thermoplastic polyurethane foam is characterized by being prepared from the following components in parts by weight:
the viscosity of the combined polyether is 300-700 mPa.s, the hydroxyl value is 100-200 mgKOH/g, and the mass percentage of water is 6.0-7.0%.
7. The thermoplastic polyurethane foam according to claim 6, wherein: the weight ratio of the cell opener to the polyol is 0.5: 100.
8. the thermoplastic polyurethane foam according to claim 6, wherein: the isocyanate is polyphenyl polymethylene polyisocyanate.
9. A process for preparing a thermoplastic polyurethane foam according to claim 6, wherein: weighing the combined polyether polyol, the polyester polyol, the organic silicon surfactant and the pore-forming agent according to the mass ratio, and fully mixing to prepare the composition; then the composition and isocyanate are fully mixed according to the proportion and poured into a special mould for reaction and foaming to prepare the thermoplastic polyurethane foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010391176.XA CN111518306A (en) | 2020-05-11 | 2020-05-11 | Cell opening agent, thermoplastic polyurethane foam and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010391176.XA CN111518306A (en) | 2020-05-11 | 2020-05-11 | Cell opening agent, thermoplastic polyurethane foam and preparation method thereof |
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| CN111518306A true CN111518306A (en) | 2020-08-11 |
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| CN202010391176.XA Withdrawn CN111518306A (en) | 2020-05-11 | 2020-05-11 | Cell opening agent, thermoplastic polyurethane foam and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4212565A1 (en) * | 2022-01-12 | 2023-07-19 | Sunko Ink Co., Ltd. | Thermoplastic polyurethane foam and impact resistant composite laminate comprising the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929646A (en) * | 1988-04-26 | 1990-05-29 | The Dow Chemical Company | Polyurethane foam prepared using high functionality cell openers |
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
| CN104987524A (en) * | 2015-08-13 | 2015-10-21 | 上海麦浦新材料科技有限公司 | Active openings agent, reticulated urethane foam material and preparation methods for active openings agent and reticulated urethane foam material |
| CN105315448A (en) * | 2015-11-25 | 2016-02-10 | 山东一诺威新材料有限公司 | Preparation method of opening agent for high resilience polyurethane foam |
| CN110283323A (en) * | 2019-06-26 | 2019-09-27 | 上海麦浦新材料科技有限公司 | A kind of silicone copolymer surfactants and its application |
| CN111040229A (en) * | 2019-12-27 | 2020-04-21 | 江苏美思德化学股份有限公司 | Open-cell type organic silicon surfactant, preparation method and application thereof, and high-resilience foam |
-
2020
- 2020-05-11 CN CN202010391176.XA patent/CN111518306A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929646A (en) * | 1988-04-26 | 1990-05-29 | The Dow Chemical Company | Polyurethane foam prepared using high functionality cell openers |
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
| CN104987524A (en) * | 2015-08-13 | 2015-10-21 | 上海麦浦新材料科技有限公司 | Active openings agent, reticulated urethane foam material and preparation methods for active openings agent and reticulated urethane foam material |
| CN105315448A (en) * | 2015-11-25 | 2016-02-10 | 山东一诺威新材料有限公司 | Preparation method of opening agent for high resilience polyurethane foam |
| CN110283323A (en) * | 2019-06-26 | 2019-09-27 | 上海麦浦新材料科技有限公司 | A kind of silicone copolymer surfactants and its application |
| CN111040229A (en) * | 2019-12-27 | 2020-04-21 | 江苏美思德化学股份有限公司 | Open-cell type organic silicon surfactant, preparation method and application thereof, and high-resilience foam |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4212565A1 (en) * | 2022-01-12 | 2023-07-19 | Sunko Ink Co., Ltd. | Thermoplastic polyurethane foam and impact resistant composite laminate comprising the same |
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Application publication date: 20200811 |