Environment-friendly combined polyether and polyurethane foam for ultralow-temperature incubator and preparation method thereof
阅读说明：本技术 环境友好型超低温保温箱用组合聚醚、聚氨酯泡沫及其制备方法 (Environment-friendly combined polyether and polyurethane foam for ultralow-temperature incubator and preparation method thereof ) 是由 李明 李春丽 李学庆 于 2020-12-28 设计创作，主要内容包括：本申请涉及一种组合聚醚,其包括如下按照重量份数计的各组分：50-60份聚醚多元醇A、30-40份聚醚多元醇B、10-15份聚酯多元醇C、2-3份泡沫稳定剂、3-5份催化剂、13-15份发泡剂和2.0-2.3份水；所述发泡剂为HFO-1233zd和HFO-1234ze的混合物,所述HFO-1233zd的含量为70-80％,所述HFO-1234ze的含量为20-30％,上述百分比为相对于发泡剂总量的质量百分比。本申请还涉及一种由上述组合聚醚和异氰酸酯制成的聚氨酯泡沫及其制备方法。利用本文所述的组合聚醚制备的聚氨酯泡沫具有优异的超低温尺寸稳定性和较低的导热系数。(The application relates to a combined polyether, which comprises the following components in parts by weight: 50-60 parts of polyether polyol A, 30-40 parts of polyether polyol B, 10-15 parts of polyester polyol C, 2-3 parts of foam stabilizer, 3-5 parts of catalyst, 13-15 parts of foaming agent and 2.0-2.3 parts of water; the foaming agent is a mixture of HFO-1233zd and HFO-1234ze, the content of HFO-1233zd is 70-80%, the content of HFO-1234ze is 20-30%, and the percentages are mass percentages relative to the total amount of the foaming agent. The application also relates to a polyurethane foam prepared from the combined polyether and isocyanate and a preparation method thereof. Polyurethane foams prepared using the conjugate polyethers described herein have excellent ultra-low temperature dimensional stability and low thermal conductivity.)
1. The composite polyether is characterized by comprising the following components in parts by weight: 50-60 parts of polyether polyol A, 30-40 parts of polyether polyol B, 10-15 parts of polyester polyol C, 2-3 parts of foam stabilizer, 3-5 parts of catalyst, 13-15 parts of foaming agent and 2.0-2.3 parts of water;
the foaming agent is a mixture of HFO-1233zd and HFO-1234ze, the content of HFO-1233zd is 70-80%, the content of HFO-1234ze is 20-30%, the above percentages are mass percentages relative to the total amount of the foaming agent;
the polyether polyol A is polyether polyol with the viscosity of 38000-48000mPa & s and the hydroxyl value of 470-520 mgKOH/g;
the polyether polyol B is polyether polyol with the viscosity of 6500-11500mPa & s and the hydroxyl value of 360-400 mgKOH/g;
the polyester polyol C is polyester polyol with the viscosity of 900-1500mPa & s and the hydroxyl value of 390-420 mgKOH/g;
the viscosities of the polyether polyol a, the polyether polyol B, the polyester polyol C, and the polyether polyol D are all 25 ℃.
2. The composite polyether of claim 1, wherein the composite polyether comprises the following components in parts by weight: 50-60 parts of polyether polyol A, 30-40 parts of polyether polyol B, 10-15 parts of polyester polyol C, 2-3 parts of foam stabilizer, 1.5-2 parts of catalyst, 13-14 parts of foaming agent and 2.0-2.3 parts of water.
3. The conjugate polyether as claimed in claim 1 or 2, wherein the polyether polyol a is a polyether polyol of type YT-600 produced by orthodox polyurethane products ltd, which has a moisture content of generally 0.1% or less in percentage by mass of water with respect to the total mass of the polyether polyol a;
the polyether polyol B is a polyether polyol which is produced by Shanghai Dongda chemical Co., Ltd and is named as Donol R4037, the moisture content of the polyether polyol B is generally less than 0.1%, and the percentage is that the mass of water accounts for the total mass of the polyether polyol C;
the polyester polyol C is produced by Nanjing Spiral and has a PS-4051 trademark, the water content is generally below 0.1%, and the percentage is that the mass of water accounts for the total mass of the polyester polyol C.
4. The composite polyether of claim 1 or 2, wherein the catalyst is a composite catalyst of POLYCAT 218, POLYCAT 211 and TMR-18, the composite catalyst is a mixture of POLYCAT 218, POLYCAT 211 and TMR-18, wherein the mass ratio of POLYCAT 218, POLYCAT 211 and TMR-18 is 1 (1-2) to (1-2).
5. The composite polyether of claim 1 or 2, wherein the foam stabilizer is a silicone-based foam stabilizer;
the water is deionized water.
6. A polyurethane foam, characterized in that the polyurethane foam is prepared from an A component and a B component, wherein the A component is the combined polyether of any one of claims 1-5;
the component B is isocyanate;
the mass ratio of the component A to the component B is 1:1.1-1: 1.3.
7. The polyurethane foam according to claim 6, wherein the mass ratio of the A-component to the B-component is from 1:1.15 to 1:1.25, preferably 1: 1.2.
8. The polyurethane foam according to claim 6 or 7, wherein the isocyanate is polymeric diphenylmethane diisocyanate, which is 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; more preferably, the polymeric MDI is model PM200 polymeric MDI made by petunia.
9. A process for preparing a polyurethane foam as claimed in any one of claims 6 to 8, which comprises mixing said A-side component and said B-side component and foaming to obtain said polyurethane foam.
10. The method of claim 9, wherein the foaming is performed using a high pressure foaming machine;
the foaming temperature is 16-20 ℃, preferably 18 ℃.
Technical Field
The present application relates to the field of polyurethane technology. Specifically, the application relates to composite polyether and polyurethane foam for an environment-friendly ultralow-temperature incubator and a preparation method thereof.
Background
The temperature of the traditional refrigerator is 16-18 ℃ below zero when the traditional refrigerator works normally, and the requirement of most people can be met. But more and more specific materials are tested and preserved at low temperatures, such as: the storage temperature of blood plasma, biological materials, vaccines, reagents, biological products, chemical reagents, strains, biological samples and the like is required to be 50-150 ℃. The function and the demand of the ultra-low temperature storage box are more and more increased, the low temperature heat preservation materials such as a refrigerator and a freezer and the like adopt polyurethane foam at present, and the traditional polyurethane foam foaming agent adopts cyclopentane, HCFC-141b, HFC-245fa, HFC-365mfc, HFC-134a and the like. The dimensional stability of foam under the ultralow temperature environment can not be guaranteed by taking cyclopentane as a basic foaming agent, the ODP value of HCFC-141b is not zero, and the ODP values of HFC-245fa, HFC-365mfc and HFC-134a as third-generation foaming agents are zero, but the GWP values are all above 800, and the elimination is faced.
Therefore, the development of an environment-friendly polyether composition for an ultra-low temperature incubator is urgently needed.
Disclosure of Invention
The application aims to provide the environment-friendly ultra-low temperature incubator with the combined polyether, so that the technical problem in the prior art is solved.
The present application also aims to provide a method for preparing the composite polyether.
It is also an object of the present application to provide a polyurethane foam made from the above-described conjugate polyether and isocyanate.
It is also an object of the present application to provide a process for the preparation of a polyurethane foam 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 composite polyether, characterized in that the composite polyether comprises the following components in parts by weight: 50-60 parts of polyether polyol A, 30-40 parts of polyether polyol B, 10-15 parts of polyester polyol C, 2-3 parts of foam stabilizer, 3-5 parts of catalyst, 13-15 parts of foaming agent and 2.0-2.3 parts of water;
the foaming agent is a mixture of HFO-1233zd and HFO-1234ze, the content of HFO-1233zd is 70-80%, the content of HFO-1234ze is 20-30%, the above percentages are mass percentages relative to the total amount of the foaming agent;
the polyether polyol A is polyether polyol with the viscosity of 38000-48000mPa & s and the hydroxyl value of 470-520 mgKOH/g;
the polyether polyol B is polyether polyol with the viscosity of 6500-11500mPa & s and the hydroxyl value of 360-400 mgKOH/g;
the polyester polyol C is polyester polyol with the viscosity of 900-1500mPa & s and the hydroxyl value of 390-420 mgKOH/g;
the viscosities of the polyether polyol a, the polyether polyol B, the polyester polyol C, and the polyether polyol D are all 25 ℃.
In one embodiment of the first aspect, the conjugate polyether comprises the following components in parts by weight: 50-60 parts of polyether polyol A, 30-40 parts of polyether polyol B, 10-15 parts of polyester polyol C, 2-3 parts of foam stabilizer, 1.5-2 parts of catalyst, 13-14 parts of foaming agent and 2.0-2.3 parts of water.
In one embodiment of the first aspect, the polyether polyol a is a polyether polyol manufactured by orthodox polyurethane products ltd under the designation YT-600, which typically has a moisture content of 0.1% or less, the percentage being the mass of water as a percentage of the total mass of the polyether polyol a;
the polyether polyol B is a polyether polyol which is produced by Shanghai Dongda chemical Co., Ltd and is named as Donol R4037, the moisture content of the polyether polyol B is generally less than 0.1%, and the percentage is that the mass of water accounts for the total mass of the polyether polyol C;
the polyester polyol C is produced by Nanjing Spiral and has a PS-4051 trademark, the water content is generally below 0.1%, and the percentage is that the mass of water accounts for the total mass of the polyester polyol C.
In one embodiment of the first aspect, the catalyst is a POLYCAT 218, POLYCAT 211, and TMR-18 composite catalyst, which is a mixture of POLYCAT 218, POLYCAT 211, and TMR-18, wherein the mass ratio of POLYCAT 218, POLYCAT 211, and TMR-18 is 1 (1-2) to (1-2).
In one embodiment of the first aspect, the foam stabilizer is a silicone-based foam stabilizer;
the water is deionized water.
In a second aspect, the present application provides a polyurethane foam characterized in that the polyurethane foam is made from an a-component which is the conjugate polyether of 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.
In one embodiment of the second aspect, the mass ratio of the a-component and the B-component is 1:1.15 to 1:1.25, preferably 1: 1.2.
In one embodiment of the second aspect, the isocyanate is polymeric diphenylmethane diisocyanate, which 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; more preferably, the polymeric MDI is model PM200 polymeric MDI made by petunia.
In a third aspect, the present application provides a method of producing the polyurethane foam of the second aspect, wherein the method comprises mixing the a-component and the B-component, and foaming to produce the polyurethane foam.
In one embodiment of the third aspect, the apparatus used in the foaming is a high pressure machine;
the foaming temperature is 16-20 ℃, preferably 18 ℃.
Compared with the prior art, the invention has the advantages that: (1) compared with the conventional polyurethane foam product, the polyurethane foam product has higher ultralow-temperature dimensional stability;
(2) compared with the conventional ultralow-temperature polyurethane foam product, the polyurethane foam product is environment-friendly and pollution-free;
(3) compared with the conventional polyester, the low-thermal-conductivity polyester has stronger foam early-stage nucleation capability through structural optimization, smaller diameter of foam holes under a scanning electron microscope, finer foam holes, stronger foam thermal radiation and lower thermal conductivity.
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 a first aspect, the present application provides a composite polyether, which comprises the following components in parts by weight: 50-60 parts of polyether polyol A, 30-40 parts of polyether polyol B, 10-15 parts of polyester polyol C, 2-3 parts of foam stabilizer, 3-5 parts of catalyst, 13-15 parts of foaming agent and 2.0-2.3 parts of water;
the foaming agent is a mixture of HFO-1233zd and HFO-1234ze, the content of HFO-1233zd is 70-80%, the content of HFO-1234ze is 20-30%, and the percentages are mass percentages relative to the total amount of the foaming agent.
The polyether polyol A is polyether polyol with the viscosity of 38000-48000mPa & s and the hydroxyl value of 470-520 mgKOH/g;
the polyether polyol B is polyether polyol with the viscosity of 6500-11500mPa & s and the hydroxyl value of 360-400 mgKOH/g;
the polyester polyol C is polyester polyol with the viscosity of 900-1500mPa & s and the hydroxyl value of 390-420 mgKOH/g;
the viscosities of the polyether polyol a, the polyether polyol B, the polyether polyol C and the polyether polyol D are all 25 ℃.
The viscosities of the polyether polyol a, the polyether polyol B and the polyester polyol C 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 polyether polyol A is polyether polyol which is produced by the general polyurethane products company Limited and has the trademark YT-600, the moisture content of the polyether polyol A is generally less than 0.1 percent, and the percentage is that the mass of water accounts for the total mass of the polyether polyol A.
Preferably, the polyether polyol B is a polyether polyol produced by Shanghai Dongdong chemical Co., Ltd under the trademark DonolR4037, and the moisture content is generally less than 0.1%, wherein the percentage is the mass of water in the total mass of the polyether polyol C.
Preferably, the polyester polyol C is a polyester polyol produced by Nanjing Spiral and having a PS-4051 trademark, the water content of the polyester polyol C is generally less than 0.1%, and the percentage is the mass of water in the total mass of the polyester polyol C.
The foam stabilizer may be a foam stabilizer conventional in the art, and preferably a silicone-based foam stabilizer. Preferably, the silicone foam stabilizer is a silicone foam stabilizer with a trade name of S-884 manufactured by Shanghai Maipu New Material science and technology company Limited.
The catalyst cannot be used with catalysts conventional in the art, and is directed to HFO-1233zd storage stability problems. Preferably, the catalyst is a composite catalyst of POLYCAT 218, POLYCAT 211 and TMR-18. The composite catalyst is a mixture of POLYCAT 218, POLYCAT 211 and TMR-18. Preferably, in the composite catalyst, the mass ratio of the POLYCAT 218, the POLYCAT 211 and the TMR-18 is 1 (1-2) to (1-2).
Preferably, the water is deionized water.
Preferably, the polyether polyol A is used in an amount of 50-60 parts; the using amount of the polyether polyol B is 30-40 parts; the using amount of the polyester polyol C is 10-15 parts; the dosage of the foam stabilizer is 2-3 parts; the dosage of the catalyst is 1.5-2 parts; the amount of the foaming agent is 14-15 parts; and the amount of the water is 2.0 to 2.3 parts.
In one embodiment, the conjugate polyether of the present invention can be prepared according to conventional preparation methods in the art, for example, by mixing the components of the raw material composition of the conjugate polyether except the foaming agent uniformly, pressurizing to 0.1Mpa in a sealed container, cooling to below 15 ℃, and adding the foaming agent mixture from the bottom of a reaction kettle through a pipeline to mix uniformly. 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 a second aspect, the present invention also provides a polyurethane foam made from 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.
Preferably, the polyurethane foam is a rigid polyurethane foam.
In a third aspect, the present invention also provides a method for 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 foaming apparatus is a high-pressure foaming machine.
Preferably, the foaming temperature is 16-20 ℃, e.g. 18 ℃.
The polyurethane foam can be used as a polyurethane foam heat-insulating material of an ultra-low temperature storage box, according to the common knowledge in the field, when the polyurethane foam is used, the component A and the component B are not mixed before use, and are mixed and used immediately, and are injected between a shell and an inner container for foaming.
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 YT-600, available from Normal open-end polyurethane products, Inc.
Polyether polyol Donol R4037 is available from Shanghai east university of chemical Co.
Polyether polyol PS-4051 is available from stevion (south kyo) chemical limited.
The silicone foam stabilizer S-884 was purchased from Shanghai Maipu New Material science and technology, Inc.
Isocyanate is polymeric MDI available from Tantario, model PM 200.
Blowing agents HFO-1233zd and HFO-1234ze are available from Honeywell (China) Inc.
Catalysts POLYCAT 218, POLYCAT 211, and TMR-18 were purchased from Woodford Technology, Inc. (Shanghai).
Examples 1 to 3
The weight parts of the raw material composition of the conjugate polyether and the isocyanate in examples 1 to 3 are specifically shown in table 1.
TABLE 1 parts by weight of the components of the raw material composition of the conjugate polyether and of the isocyanate in examples 1 to 3
The following raw materials except isocyanate are combined polyether
Example 1
Example 2
Example 3
Polyether polyol YT-600
50
55
60
Polyether polyol Donol R4037
40
30
30
Polyester polyol PS-4051
10
15
10
Foam stabilizer S-884
2
2.5
3
POLYCAT 218
0.4
0.5
0.6
POLYCAT 211
0.8
0.7
0.6
TMR-18
0.6
0.8
0.6
Deionized water
2.0
2.15
2.3
HFO-1233zd
9.8
10.8
12
HFO-1234ze
4.2
3.7
3
Combined polyether general component
119.8
121.15
122.1
Isocyanate PM200
149.8
145.4
140.4
(1) Preparation of conjugate polyether
The preparation method comprises the following steps of uniformly mixing all components of the raw material composition of the combined polyether except the foaming agent, pressurizing by a sealed container to 0.1Mpa, cooling to below 15 ℃, and adding the foaming agent mixture from the bottom of a reaction kettle through a pipeline to be uniformly mixed.
(2) Preparation of polyurethane foams
And (2) reacting the combined polyether with isocyanate at 18 ℃ according to a ratio, and injecting the mixture into a mould to prepare the hard polyurethane foam heat-insulating material for the heat-insulating box.
Effects of the embodiment
The polyurethane foams made in examples 1-3 were compared to the comparative products and the results are shown in Table 2 below.
TABLE 2 Performance data for polyurethane foams according to 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.