CN110885416A - High-density block foam polyurethane material and preparation method thereof - Google Patents
High-density block foam polyurethane material and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
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- C08G2101/00—Manufacture of cellular products
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention belongs to the technical field of polyurethane application, and particularly relates to a high-density block foam polyurethane material and a preparation method thereof. The high-density block foam polyurethane material is prepared from a component A and a component B, wherein: the component A is prepared from polyether polyol A, polyether polyol B, polyester polyol C, a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer; the component B is polymeric diphenylmethane diisocyanate. The high-density block foam polyurethane material is environment-friendly, and has good finished product strength and uniform density distribution; the preparation method is scientific, reasonable, simple and feasible.
Description
Technical Field
The invention belongs to the technical field of polyurethane application, and particularly relates to a high-density block foam polyurethane material and a preparation method thereof.
Background
At present, the processing mode of rigid polyurethane plastic products is in a transformation stage, the traditional special customized mould and the personalized product processing mode face the problem of low production efficiency, more and more rigid polyurethane production and processing manufacturers are changed from a one-time processing and forming mode to a mode of firstly producing large blocks of polyurethane foam and then cutting and processing, and then polyurethane products with uniform density distribution are obtained.
The foaming process of the polyurethane foam is influenced by the temperature of a mould and the combination of polyether polyol components, and the difference between the overall density of the foam and the density of a foam core is 5-10kg/m3In different cases, the higher the water content in the combined polyether polyol is, the thinner the foam crust is, and the smaller the density difference is; conversely, the lower the water content in the polyether polyol, the thicker the foam crust, and the greater the density difference; the crust thickness is also affected by the mold temperature, the foaming speed. One process problem faced by cast polyurethane products is: the density difference is large, so that the deviation of the internal and external strength of the product is large, and if the material injection amount is calculated by the integral density, the core density is low, and the strength of the product is insufficient; if the core density is used to calculate the injection amount, the overall density is high, the product quality is too high, and the double pressure of cost and product weight is applied. In order to solve the above problems, more and more polyurethane processing manufacturers choose to first produce a polyurethane foam material with uniform density distribution, and then customize and cut the foam by special cutting equipment to process the foam into the required size and shape of the product.
With the gradual replacement of FCHC-141b as a blowing agent, water, pentane, and HCFC-245fa have begun to be used in the field of polyurethane foaming as new blowing agents.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, and the high-density block foam polyurethane material is environment-friendly, and has good finished product strength and uniform density distribution; the invention also provides a preparation method of the composition, which is scientific, reasonable, simple and feasible.
The high-density block foam polyurethane material is prepared from a component A and a component B, wherein:
the component A is prepared from the following raw materials in parts by weight:
the polyether polyol A is polyether polyol with the functionality of 4.6-4.8 and the hydroxyl value of 390-420 mgKOH/g;
the polyether polyol B is polyether polyol with the functionality of 3.0 and the hydroxyl value of 150-180 mgKOH/g;
the polyester polyol C is polyester polyol with a hydroxyl value of 450-470 mgKOH/g;
the component B is polymeric diphenylmethane diisocyanate.
Wherein, the preferred technical scheme is as follows:
the polyether polyol A is INOVOL R6001C, the polyether polyol B is INOVOL C310, and the polyester polyol C is ED504, which are all commercially available products from Shandong-Nowei GmbH.
The physical foaming agent is pentafluoropropane (HCFC-245fa), and the foaming agent is characterized by low boiling point, easy volatilization and fine foam generated by the foaming agent.
The chemical foaming agent is water.
The catalyst is a mixture of N, N-dimethylcyclohexylamine (Y-12), N, N-dimethylbenzylamine (Y-27), formate of 2-hydroxy-N, N, N-trimethyl-1-propylamine (TMR-2) and potassium acetate (KAc).
The foam stabilizer is L-6950, and the manufacturer comprises: mai-ji-high-new materials ltd.
The polymeric diphenylmethane diisocyanate is one of PM-200 (produced by Nicotiana Vanhua polyurethane Co., Ltd.) or M20S (produced by Pasteur Corp.).
The preparation method of the high-density block foam polyurethane material comprises the following steps:
(1) preparation of component A: adding polyether polyol A, polyether polyol B and polyester polyol C into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.0-1.3, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing for 12-24 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Compared with the prior art, the invention has the following beneficial effects:
1. in the invention, the three polyethers/polyesters are used in a matched manner, so that the viscosity of the combined polyether polyol system is effectively reduced, and the mixing effect of the polyether component A and the isocyanate component B in the material injection process is favorably improved.
2. According to the invention, the reaction time of A, B two components is controlled according to the parts of the catalyst, and the heat release process is controlled, so that the polyurethane foam is effectively and fully expanded, the apparent core density of the upper, middle and lower parts is uniformly distributed, the foam strength is high, and the foam holes are fine.
3. The preparation method is scientific, reasonable, simple and feasible.
Detailed Description
The present invention is further described with reference to the following examples, which are not intended to limit the practice of the invention.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Comparative example 1
The weight ratio of the component A to the component B is 1: 1.0, wherein the component A comprises the following components in parts by weight:
adding various polyether polyols into a stirring kettle in proportion, uniformly stirring, sequentially adding a weighed physical foaming agent, a weighed chemical foaming agent, a weighed catalyst and a weighed foam stabilizer into the stirring kettle in proportion, and uniformly stirring. And finishing the preparation of the component A.
Mixing the prepared component A and component B, namely diphenylmethane diisocyanate PM-200, in a ratio of 1: 1.0, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 24 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 1
The weight ratio of the component A to the component B is 1: 1.0, wherein the component A comprises the following components in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate (PM-200) for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.0 by weight ratio, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 24 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 2
The weight ratio of the component A to the component B is 1: 1.0, wherein the component A comprises the following components in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate (PM-200) for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.0 by weight ratio, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 24 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 3
The weight ratio of the component A to the component B is 1: 1.0, wherein the component A comprises the following components in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate (PM-200) for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.0 by weight ratio, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 24 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
The high density block foam polyurethane materials prepared in comparative example 1 and examples 1-3 were subjected to performance tests, the results of which are shown in table 1.
TABLE 1 test results
| Item | Comparative example 1 | Example 1 | Example 2 | Example 3 |
| Foam Density (kg/m)3) | 75 | 75 | 75 | 75 |
| Compressive Strength (kPa) | 565.3 | 609.8 | 612.4 | 610.6 |
| Coefficient of thermal conductivity (mW/m. K) | 20.42 | 19.75 | 19.87 | 20.20 |
| Top density (kg/m)3) | 72.9 | 73.2 | 73.3 | 72.8 |
| Middle Density (kg/m)3) | 71.8 | 72.2 | 72.5 | 72.1 |
| Lower part Density (kg/m)3) | 74.2 | 73.8 | 73.5 | 74.0 |
From data, the material ratio is 1: at 1.0, the density difference was the lowest when the water component was 2.3 parts and the pentafluoropropane component was 10 parts.
Comparative example 2
The weight ratio of the component A to the component B is 1: 1.15, the component A is as follows in parts by weight:
adding various polyether polyols into a stirring kettle in proportion, uniformly stirring, sequentially adding a weighed physical foaming agent, a weighed chemical foaming agent, a weighed catalyst and a weighed foam stabilizer into the stirring kettle in proportion, and uniformly stirring. And finishing the preparation of the component A.
Mixing the prepared component A and component B, namely diphenylmethane diisocyanate PM-200, in a ratio of 1: 1.15, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing for 12 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 4
The weight ratio of the component A to the component B is 1: 1.15, the component A is as follows in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: the polymeric diphenylmethane diisocyanate (M20S) was weighed for use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.15, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing for 12 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 5
The weight ratio of the component A to the component B is 1: 1.15, the component A is as follows in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: the polymeric diphenylmethane diisocyanate (M20S) was weighed for use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.15, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing for 12 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 6
The weight ratio of the component A to the component B is 1: 1.15, the component A is as follows in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: the polymeric diphenylmethane diisocyanate (M20S) was weighed for use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.15, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing for 12 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
The high density block foam polyurethane materials prepared in comparative example 2 and examples 4-6 were subjected to performance tests, the results of which are shown in table 2.
TABLE 2 test results
| Item | Comparative example 2 | Example 4 | Example 5 | Example 6 |
| Foam Density (kg/m)3) | 75 | 75 | 75 | 75 |
| Compressive Strength (kPa) | 578.6 | 643.6 | 655.3 | 652.1 |
| Coefficient of thermal conductivity (mW/m. K) | 20.21 | 19.58 | 19.69 | 19.92 |
| Top density (kg/m)3) | 72.3 | 73.0 | 73.2 | 72.9 |
| Middle Density (kg/m)3) | 71.3 | 72.2 | 72.7 | 72.1 |
| Lower part Density (kg/m)3) | 73.9 | 73.5 | 73.8 | 73.8 |
From the above table, the material ratio is 1: the density difference was the lowest when the water component was 2.3 parts at 1.15 and the pentafluoropropane component was 10 parts.
Comparative example 3
The weight ratio of the component A to the component B is 1: 1.3, the component A is as follows in parts by weight:
adding various polyether polyols into a stirring kettle in proportion, uniformly stirring, sequentially adding a weighed physical foaming agent, a weighed chemical foaming agent, a weighed catalyst and a weighed foam stabilizer into the stirring kettle in proportion, and uniformly stirring. And finishing the preparation of the component A.
Mixing the prepared component A and component B, namely diphenylmethane diisocyanate PM-200, in a ratio of 1: 1.3, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 18 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 7
The weight ratio of the component A to the component B is 1: 1.3, the component A is as follows in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate (PM-200) for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.3, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 18 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 8
The weight ratio of the component A to the component B is 1: 1.3, the component A is as follows in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate (PM-200) for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.3, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 18 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Example 9
The weight ratio of the component A to the component B is 1: 1.3, the component A is as follows in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate (PM-200) for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.3, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 18 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
Comparative example 4
The weight ratio of the component A to the component B is 1: 1.3, the component A is as follows in parts by weight:
the preparation method comprises the following steps:
(1) preparation of component A: adding polyether polyol and polyester polyol into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate (PM-200) for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.3, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing the mixture for 18 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
The high density block foam polyurethane materials prepared in comparative examples 3 to 4 and examples 7 to 9 were subjected to the performance test, and the test results are shown in table 3.
TABLE 3 test results
| Item | Comparative example 3 | Example 7 | Example 8 | Example 9 | Comparative example 4 |
| Foam Density (kg/m)3) | 75 | 75 | 75 | 75 | 75 |
| Compressive Strength (kPa) | 605.2 | 678.9 | 675.6 | 673.3 | 614.8 |
| Coefficient of thermal conductivity (mW/m. K) | 20.23 | 19.56 | 19.68 | 19.77 | 20.12 |
| Top density (kg/m)3) | 71.8 | 72.8 | 72.9 | 72.3 | 70.6 |
| Middle Density (kg/m)3) | 70.5 | 71.1 | 71.5 | 71.2 | 72.9 |
| Lower part Density (kg/m)3) | 73.9 | 73.3 | 73.1 | 73.2 | 76.1 |
From the above table, the material ratio is 1: the density difference was the lowest when the water component was 2.6 parts at 1.3 and the pentafluoropropane component was 5 parts.
Claims (8)
1. A high-density block foam polyurethane material is characterized in that: is prepared from a component A and a component B, wherein:
the component A is prepared from the following raw materials in parts by weight:
the polyether polyol A is polyether polyol with the functionality of 4.6-4.8 and the hydroxyl value of 390-420 mgKOH/g;
the polyether polyol B is polyether polyol with the functionality of 3.0 and the hydroxyl value of 150-180 mgKOH/g;
the polyester polyol C is polyester polyol with a hydroxyl value of 450-470 mgKOH/g;
the component B is polymeric diphenylmethane diisocyanate.
2. The high density block foam polyurethane material of claim 1, wherein: the polyether polyol A is INOVOL R6001C, the polyether polyol B is INOVOL C310, and the polyester polyol C is ED 504.
3. The high density block foam polyurethane material of claim 1, wherein: the physical foaming agent is HCFC-245 fa.
4. The high density block foam polyurethane material of claim 1, wherein: the chemical foaming agent is water.
5. The high density block foam polyurethane material of claim 1, wherein: the catalyst is a mixture of formate of N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, 2-hydroxy-N, N, N-trimethyl-1-propylamine and potassium acetate.
6. The high density block foam polyurethane material of claim 1, wherein: the foam stabilizer is L-6950.
7. The high density block foam polyurethane material of claim 1, wherein: the polymeric diphenylmethane diisocyanate is one of PM-200 or M20S.
8. A method of preparing a high density block foam polyurethane material according to any one of claims 1 to 7, wherein: the method comprises the following steps:
(1) preparation of component A: adding polyether polyol A, polyether polyol B and polyester polyol C into a stirring kettle, uniformly stirring, sequentially adding a physical foaming agent, a chemical foaming agent, a catalyst and a foam stabilizer into the stirring kettle, and uniformly stirring;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: b is 1: 1.0-1.3, injecting the mixture into a mold by a high-pressure foaming machine, filling and curing for 12-24 hours, and then opening the mold to obtain the high-density block foam polyurethane material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113801287A (en) * | 2021-08-02 | 2021-12-17 | 佳化化学科技发展（上海）有限公司 | Polyether composition, polyurethane rigid foam using polyether composition as raw material and preparation method of polyurethane rigid foam |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801287A (en) * | 2021-08-02 | 2021-12-17 | 佳化化学科技发展（上海）有限公司 | Polyether composition, polyurethane rigid foam using polyether composition as raw material and preparation method of polyurethane rigid foam |
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