阅读说明：本技术 低温发泡用组合聚醚、聚氨酯泡沫及其原料组合物和制备方法 (Combined polyether for low-temperature foaming, polyurethane foam, raw material composition of polyurethane foam and preparation method of polyurethane foam ) 是由 李学庆 李明 程甜 李春丽 于 2020-11-23 设计创作，主要内容包括：本申请涉及一种低温发泡用组合聚醚,其特征在于,以重量份数为基准计,包含如下原料组分：40-60份第一聚醚多元醇、35-45份第二聚醚多元醇、5-15份第三聚醚多元醇、2-3份泡沫稳定剂、5-9份催化剂、13-15份发泡剂和1.5-2.0份水。本申请还涉及包括如上所述的低温发泡用组合聚醚的聚氨酯泡沫原料组合物。本申请还涉及利用上述聚氨酯泡沫原料组合物制备的聚氨酯泡沫及其制备方法。本发明的聚氨酯泡沫制品可以在模具较低温度时与模具牢固粘结,利用本文所述的低温发泡用组合聚醚制备的聚氨酯泡沫可用作低温保温泡沫材料,具有优异的低温尺寸稳定性。(The application relates to a combined polyether for low-temperature foaming, which is characterized by comprising the following raw material components in parts by weight: 40-60 parts of first polyether polyol, 35-45 parts of second polyether polyol, 5-15 parts of third polyether polyol, 2-3 parts of foam stabilizer, 5-9 parts of catalyst, 13-15 parts of foaming agent and 1.5-2.0 parts of water. The application also relates to a polyurethane foam raw material composition comprising the combined polyether for low-temperature foaming. The application also relates to polyurethane foam prepared by using the polyurethane foam raw material composition and a preparation method thereof. The polyurethane foam product can be firmly bonded with a mold at a lower temperature, and the polyurethane foam prepared by using the combined polyether for low-temperature foaming can be used as a low-temperature heat-insulating foam material and has excellent low-temperature dimensional stability.)

1. The composite polyether for low-temperature foaming is characterized by comprising the following raw material components in parts by weight: 40-60 parts of first polyether polyol, 35-45 parts of second polyether polyol, 5-15 parts of third polyether polyol, 2-3 parts of foam stabilizer, 5-9 parts of catalyst, 13-15 parts of foaming agent and 1.5-2.0 parts of water;

the foaming agent is a cyclopentane foaming agent;

the first polyether polyol is a polyether polyol having a viscosity of 4800-6200mPa · s, a functionality of 4.5-5 and a hydroxyl value of 410-435 mgKOH/g;

the second polyether polyol is polyether polyol with the viscosity of 13000-17000mPa & s, the functionality of 4 and the hydroxyl value of 440-480 mgKOH/g;

the third polyether polyol is polyether polyol with the viscosity of 60-80mPa & s, the functionality of 2 and the hydroxyl value of 270-290 mgKOH/g;

the first polyether polyol, the second polyether polyol, and the third polyether polyol all have a viscosity of 25 ℃.

2. The polyether block for low-temperature foaming according to claim 1, wherein the first polyether polyol is used in an amount of 50 to 60 parts;

the using amount of the second polyether polyol is 35-40 parts;

the using amount of the third polyether polyol is 5-10 parts;

the dosage of the foam stabilizer is 2-2.5 parts;

the dosage of the catalyst is 6-7.5 parts;

the amount of the foaming agent is 14-15 parts; and

the amount of the water is 1.8-2.0 parts.

3. A polyether polyol composition for low temperature foaming according to claim 1 or 2, wherein the first polyether polyol is a polyether polyol having a designation NJ8206H, manufactured by sentention chemical ltd;

the second polyether polyol is a polyether polyol which is produced by Shanghai Dongda chemical Co., Ltd and has a Donol R6246 mark;

the third polyether polyol is polyether polyol which is produced by Hebei Asia east chemical group limited and has the mark number of YD-204.

4. The conjugate polyether for low-temperature foaming according to claim 1 or 2, wherein the foam stabilizer is a silicone-based foam stabilizer, preferably a silicone-based foam stabilizer having a brand number of H-3663C manufactured by jun chemical limited of shandong, zhong;

the catalyst is an amine catalyst and/or an organic metal catalyst, and the catalyst is preferably a composite catalyst of N, N ', N' -tetramethyl-1, 6-hexamethylene diamine, Dabco TMR-30 and N, N-dimethyl-benzylamine, wherein the mass ratio of the N, N, N ', N' -tetramethyl-1, 6-hexamethylene diamine, the Dabco TMR-30 and the N, N-dimethyl-benzylamine is 1 (2-4): 2-4, preferably 1 (1-3): 1-3).

5. A polyurethane foam raw material composition, which comprises an A component and a B component, wherein the A component is the low-temperature foaming composite polyether as defined in any one of claims 1-4; the component B is isocyanate; the mass ratio of the component A to the component B is 1:1.1-1:1.3, preferably 1:1.15-1: 1.25.

6. The polyurethane foam raw material composition according to claim 5, wherein the mass ratio of the A component to the B component is 1: 1.2.

7. The polyurethane foam feed composition of claim 5, wherein the isocyanate is polymeric diphenylmethane diisocyanate, preferably polymeric MDI having the model number PM200, available from Tantawa.

8. A method for preparing a polyurethane foam using the polyurethane foam starting composition of claim 5, comprising mixing the A-side component and the B-side component and foaming the mixture in a foaming device to obtain a polyurethane foam.

9. The method of claim 7, wherein the foaming device is a high pressure foaming machine;

the foaming temperature is 20-25 deg.C, preferably 22 deg.C.

10. A polyurethane foam prepared by the method of claim 8 or 9.

Technical Field

The present application relates to the field of polyurethane technology. Specifically, the application relates to a combined polyether for low-temperature foaming, polyurethane foam, a raw material composition of the combined polyether and the polyurethane foam, and a preparation method of the combined polyether and the polyurethane foam.

Background

With the development of cold chain technology, personalized and customized kitchen refrigerators gradually enter super-hotels. Due to uncertainty of appearance and size of the personalized and customized refrigerator, manufacturers basically produce the refrigerator in a splicing type mold, and part of manufacturers with smaller scale mainly use a wood mold. At present, the heating of a mould can not be effectively guaranteed in the production process of most kitchen refrigerator manufacturers, and at present, the shells of the main kitchen commercial refrigerators are mainly made of stainless steel, so that the requirement on the cohesiveness of raw materials is high, and particularly, the temperature of the mould is lower than 35 ℃, and the temperature of the mould is required to be 35-50 ℃ by the refrigerator and refrigerator manufacturers. In order to overcome the problem of weak bonding caused by lower temperature of the die, manufacturers often increase the material injection amount and prolong the die opening time, thereby reducing the production efficiency and increasing the production and manufacturing cost.

For this reason, there is a continuing need in the art to develop a conjugate polyether for low temperature foaming, a polyurethane foam, and a raw material composition and preparation method thereof.

Disclosure of Invention

The invention provides a combined polyether, polyurethane foam, a raw material composition thereof and a preparation method thereof, aiming at overcoming the defect of insufficient low-temperature foaming cohesiveness in the production of kitchen commercial refrigerators in the prior art. The polyurethane foam provided by the invention adopts the combined polyether provided by the invention, so that the adhesion of the foam and a steel plate after the combined polyether reacts in a low-temperature mold is obviously improved.

The present application aims to provide a conjugate polyether for low temperature foaming, thereby solving the above-mentioned technical problems in the prior art.

The present application also provides a polyurethane foam raw material composition comprising the above-mentioned polyether composition for low-temperature foaming.

It is also an object of the present invention to provide a method for preparing a polyurethane foam using the above polyurethane foam raw material composition.

It is also an object of the present application to provide a polyurethane foam prepared by the process as described above.

In order to solve the above technical problems, the present application provides the following technical solutions.

In a first aspect, the present application provides a combined polyether for low temperature foaming, which comprises the following raw material components in parts by weight: 40-60 parts of first polyether polyol, 35-45 parts of second polyether polyol, 5-15 parts of third polyether polyol, 2-3 parts of foam stabilizer, 5-9 parts of catalyst, 13-15 parts of foaming agent and 1.5-2.0 parts of water;

the foaming agent is a cyclopentane foaming agent;

the first polyether polyol is a polyether polyol having a viscosity of 4800-6200mPa · s, a functionality of 4.5-5 and a hydroxyl value of 410-435 mgKOH/g;

the second polyether polyol is polyether polyol with the viscosity of 13000-17000mPa & s, the functionality of 4 and the hydroxyl value of 440-480 mgKOH/g;

the third polyether polyol is polyether polyol with the viscosity of 60-80mPa & s, the functionality of 2 and the hydroxyl value of 270-290 mgKOH/g;

the first polyether polyol, the second polyether polyol, and the third polyether polyol all have a viscosity of 25 ℃.

In one embodiment of the first aspect, the first polyether polyol is used in an amount of 50 to 60 parts;

the using amount of the second polyether polyol is 35-40 parts;

the using amount of the third polyether polyol is 5-10 parts;

the dosage of the foam stabilizer is 2-2.5 parts;

the dosage of the catalyst is 6-7.5 parts;

the amount of the foaming agent is 14-15 parts; and

the amount of the water is 1.8-2.0 parts.

In one embodiment of the first aspect, the first polyether polyol is a polyether polyol manufactured by sentry-walling-ningwu chemical company, inc under the designation NJ 8206H;

the second polyether polyol is a polyether polyol which is produced by Shanghai Dongda chemical Co., Ltd and has a Donol R6246 mark;

the third polyether polyol is polyether polyol which is produced by Hebei Asia east chemical group limited and has the mark number of YD-204.

In one embodiment of the first aspect, the foam stabilizer is a silicone-based foam stabilizer, preferably a silicone-based foam stabilizer manufactured by Jun chemical Co., Ltd, Zhongshan Dong under the brand name H-3663C;

the catalyst is an amine catalyst and/or an organic metal catalyst, and is preferably a composite catalyst of N, N ', N' -tetramethyl-1, 6-hexanediamine, Dabco TMR-30 and N, N-dimethyl-benzylamine, wherein the mass ratio of the N, N, N ', N' -tetramethyl-1, 6-hexanediamine, the Dabco TMR-30 and the N, N-dimethyl-benzylamine is 1: 2-4, preferably 1: 1-3.

In a second aspect, the present application provides a polyurethane foam raw material composition comprising an a-component and a B-component, characterized in that the a-component is the low temperature foaming conjugate polyether as described in the first aspect; the component B is isocyanate; the mass ratio of the component A to the component B is 1:1.1-1:1.3, preferably 1:1.15-1: 1.25.

In one embodiment of the second aspect, the mass ratio of the A component to the B component is 1: 1.2.

In one embodiment of the second aspect, the isocyanate is polymeric diphenylmethane diisocyanate, preferably polymeric MDI model PM200, manufactured by petunia.

In a third aspect, the present application provides a method for producing a polyurethane foam using the polyurethane foam raw material composition according to the second aspect, characterized in that the method comprises mixing the a-component and the B-component, and then foaming in a foaming device to produce a polyurethane foam.

In one embodiment of the third aspect, the foaming device is a high pressure foaming machine.

In an embodiment of the third aspect, the foaming temperature is 20-25 ℃, preferably 22 ℃.

In a fourth aspect, the present application provides a polyurethane foam prepared by the method as described in the third aspect.

Compared with the prior art, the invention has the advantages that: the polyurethane foam product can be firmly bonded with a mold at a lower temperature, and the polyurethane foam prepared by using the combined polyether for low-temperature foaming can be used as a low-temperature heat-insulating foam material and has excellent low-temperature dimensional stability.

Detailed Description

Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.

When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.

The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.

In one embodiment, the present invention provides a conjugate polyether comprising the following components in parts by weight: 40-60 parts of first polyether polyol, 35-45 parts of second polyether polyol, 5-15 parts of third polyether polyol, 2-3 parts of foam stabilizer, 4-6 parts of catalyst, 13-15 parts of foaming agent and 1.5-2.0 parts of water. In a preferred embodiment, the first polyether polyol is used in an amount of 50 to 60 parts; the using amount of the second polyether polyol is 35-40 parts; the using amount of the third polyether polyol is 5-10 parts; the dosage of the foam stabilizer is 2-2.5 parts; the dosage of the catalyst is 6-7.5 parts; the amount of the foaming agent is 14-15 parts; and the amount of the water is 1.8-2.0 parts.

Polyether polyols

Polyether polyols are oligomers which contain ether linkages (-R-O-R-) in the main chain and more than 2 hydroxyl groups (-OH) in the terminal or pendant groups. The polyether polyol is prepared by ring opening polymerization of low molecular weight polyol, polyamine or compound containing active hydrogen as initiator and olefin oxide under the action of catalyst. The alkylene oxides are mainly propylene oxide (propylene oxide) and ethylene oxide (ethylene oxide), of which propylene oxide is the most important. The polyhydric alcohol initiator includes dihydric alcohol such as propylene glycol and ethylene glycol, trihydric alcohol such as glycerin trimethylolpropane, and polyhydric alcohol such as pentaerythritol, tetrol, xylitol, sorbitol, and sucrose; the amine initiator is diethylamine, diethylenetriamine, etc.

In one embodiment, the first polyether polyol is a polyether polyol having a viscosity of 4800-. In one embodiment, the second polyether polyol is a polyether polyol having a viscosity of 13000-17000mPa · s, a functionality of 4, and a hydroxyl value of 440-480 mgKOH/g; in one embodiment, the third polyether polyol is a polyether polyol having a viscosity of 60 to 80mPa · s, a functionality of 2 and a hydroxyl value of 270 and 290 mgKOH/g. The first polyether polyol, the second polyether polyol, and the third polyether polyol all have a viscosity of 25 ℃. In one embodiment, the viscosity of the first polyether polyol, the second polyether polyol, and the third polyether polyol may each independently be a viscosity conventional in the art, such as a kinematic viscosity. The kinematic viscosity is typically measured using a rotational viscometer.

Preferably, the first polyether polyol is a polyether polyol produced by sentry-kongmu chemical limited under the trade name NJ8206H, and the moisture content of the polyether polyol is generally less than 0.1%, wherein the percentage is the mass of water in percentage of the total mass of the first polyether polyol.

Preferably, the second polyether polyol is a polyether polyol manufactured by Shanghai Dongda chemical Co., Ltd under the trade name of Donol R6246, and the moisture content is generally below 0.1%, wherein the percentage is the mass of water in the total mass of the second polyether polyol.

The Donol R6246 is a hard foam polyether polyol, belongs to polyether polyol which has high functionality, low heat conductivity coefficient, good cohesiveness and the like, has the characteristics of high bonding strength, good fluidity and strong pressure resistance, and is widely applied to polyurethane hard foam products, such as plate materials, refrigerators and freezers, building heat preservation, cold chain industry and the like.

The basic product properties of Donol R6246 are as follows:

performance of	Parameter(s)
		Appearance of the product	Light yellow transparent liquid
Water content (%)	≤0.20
		Hydroxyl value (mgKOH/g)	440-480
Acid value (mgKOH/g)	≤0.15
		pH (isopropanol)	9.0-13.0
Viscosity (25 ℃ C.) mPa.s	13000-17000
		Chroma (GD)	≤6

。

Preferably, the third polyether polyol is polyether polyol which is produced by the chemical group limited of northeast Asia east Hebei and has the mark of YD-204, the moisture content of the polyether polyol is generally less than 0.1 percent, and the percentage is that the mass of water accounts for the total mass of the third polyether polyol.

In one embodiment, the blowing agent is cyclopentane, such as cyclopentane, n-pentane, and isopentane.

In one embodiment, the water is deionized water. In one embodiment, the foam stabilizer may be a foam stabilizer conventional in the art, preferably a silicone-based foam stabilizer. Preferably, the silicone foam stabilizer is a silicone foam stabilizer with the brand number of H-3663C, which is produced by Jun chemical Co., Ltd.

In one embodiment, the catalyst may be a catalyst conventional in the art, preferably an amine catalyst and/or an organometallic catalyst. Preferably, the amine catalyst is a tertiary amine catalyst. Preferably, the tertiary amine catalyst is a composite catalyst of N, N, N ', N' -tetramethyl-1, 6-hexanediamine (WSDW-CT-TMHDA), Dabco TMR-30 and N, N-dimethyl-benzylamine. The composite catalyst is a mixture of N, N-dimethylcyclohexylamine, Dabco TMR-30 and N, N-dimethyl-benzylamine. Preferably, in the composite catalyst, the mass ratio of the N, N, N ', N' -tetramethyl-1, 6-hexanediamine to the Dabco TMR-30 to the N, N-dimethyl-benzylamine is 1: 2-4, and more preferably 1: 1-3.

The composite polyether of the present invention can be prepared according to conventional preparation methods in the art, for example, by uniformly mixing the components of the raw material composition of the composite polyether. Preferably, the mixing is performed in a mixing vessel having a safety device. Preferably, the mixing vessel is a mixing kettle. Preferably, the mixing is performed in a stainless steel vessel. Preferably, the mixing is performed under stirring conditions. Preferably, the mixing time is 0.5 to 1 hour, such as 0.75 hour.

In one embodiment, the present invention also provides a polyurethane foam feedstock composition comprising an a-component and a B-component; the component A is the combined polyether; the component B is isocyanate; the mass ratio of the component A to the component B is 1:1.1-1: 1.3.

Preferably, the mass ratio of the A component to the B component is 1:1.15 to 1:1.25, for example 1: 1.2.

Preferably, the isocyanate is polymeric diphenylmethane diisocyanate (polymeric MDI for short). The polymeric diphenylmethane diisocyanate refers to a mixture of pure diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate. Preferably, in the product of the polymeric diphenylmethane diisocyanate, the content of the polymeric diphenylmethane diisocyanate is 51.3%, and the percentage is mass percent.

Preferably, the polymeric MDI is model PM200 polymeric MDI made by petunia.

In one embodiment, the present invention also provides a method of preparing a polyurethane foam comprising the steps of: and mixing the component A and the component B, and foaming to prepare polyurethane foam.

The conditions for the preparation process of the polyurethane foam may be various conditions conventional in the art.

Preferably, the apparatus used for foaming is a high pressure foaming machine.

Preferably, the foaming temperature is 20-25 ℃, e.g. 22 ℃.

The polyurethane foam can be used as a foam heat-insulating material for low-temperature foaming, and according to the common knowledge in the field, when the polyurethane foam is applied, the A component and the B component are not mixed before use, and are mixed immediately before use, and are injected between a shell and an inner container for foaming.

In one embodiment, the present invention also provides a polyurethane foam prepared by the method of preparing a polyurethane foam.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The percentage in the invention is the mass percentage of each component in the total amount of the raw materials.

Examples

The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The sources of the raw materials used in the following examples are as follows:

polyether polyol NJ8206H, available from Tanshun chemical Co., Ltd.

The polyether polyol Donol R6246 is available from Shanghai east Chemicals, Inc.

Polyether polyol YD-204 was purchased from Yato chemical group, Inc.

Silicone foam stabilizer H-3663C is available from Jun chemical Co., Ltd, east China.

Isocyanate is polymeric MDI available from Tantario, model PM 200.

In the effect examples, the standards followed for polyurethane foam performance testing are as follows:

core density: GB/T6343;

low-temperature dimensional stability: GB/T8811.

Preparation examples of conjugate polyethers

Examples 1 to 3

Examples 1-3 relate to the preparation of a combination polyether for low temperature foaming.

In examples 1 to 3, the procedure for preparing the conjugate polyether comprised uniformly mixing the components except isocyanate in a stainless steel mixing tank at room temperature for 45min according to the formulation shown in Table 1, and stirring uniformly.

Table 1 parts by weight of the components of the raw material composition of the conjugate polyether and the isocyanate in examples 1-3.

Raw material components	Example 1	Example 2	Example 3
				Polyether polyol NJ8206H	40	50	60
Polyether polyol Donol R6246	45	40	35
				Polyether polyol YD-204	15	10	5
Foam stabilizer H-3663C	2	2.5	3
				N, N, N ', N' -tetramethyl-1, 6-hexanediamine	1.5	2	1.5
Dabco TMR-30	2	2	3
				N, N dimethyl-benzylamine	3	2	3
Deionized water	1.5	1.8	2.0
				Cyclopentane	15	14	13
Combined polyether general component	125	124.3	125.5
				Isocyanate PM200	156.3	149.2	144.3

Effects of the embodiment

This example relates to the preparation of polyurethane foams.

The preparation steps of the polyurethane foam comprise that the combined polyether and isocyanate in the embodiment 1-3 are reacted at 22 ℃ according to the proportion, injected into a mould and foamed to prepare the rigid polyurethane foam heat insulation material for the refrigerator.

The polyurethane foams made using the conjugate polyethers of examples 1-3 were each tested and the results are shown in Table 2 below.

Table 2 polyurethane foam performance parameters prepared using the conjugate polyethers of examples 1-3.

As can be seen from Table 2, the polyurethane foams obtained according to the present invention have higher compressive strength, better dimensional stability at low temperatures and lower thermal conductivity.

The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.