CN113461893B

CN113461893B - Polyether for heat preservation of refrigerator/freezer and method for preparing polyurethane rigid foam by using polyether

Info

Publication number: CN113461893B
Application number: CN202011611585.2A
Authority: CN
Inventors: 武亚东; 顾志宏; 杨煜明; 冀国进; 张亮
Original assignee: Hebei Yadong Chemical Group Co ltd
Current assignee: Hebei Yadong Chemical Group Co ltd
Priority date: 2020-12-30
Filing date: 2020-12-30
Publication date: 2023-02-21
Anticipated expiration: 2040-12-30
Also published as: CN113461893A

Abstract

The invention belongs to the technical field of heat insulation materials, and provides composite polyether for heat insulation of a refrigerator/a freezer and a method for preparing polyurethane rigid foam by using the composite polyether, wherein the composite polyether comprises 40-75 parts by weight of high-functionality polyether, 10-40 parts by weight of amino polyether, 0-20 parts by weight of polyol, 1-3.5 parts by weight of organic silicon surfactant, 1.2-3.2 parts by weight of water, 3-30 parts by weight of cis-1-chloro-2-, 3-tetrafluoropropene (HFO-1224 yd), 0-15 parts by weight of C4-C5 hydrocarbon foaming agent and 1.5-5 parts by weight of catalyst. By adopting the technical scheme, the problems that the polyurethane composite material produced by the foaming agent composition in the prior art is still not ideal in heat conductivity coefficient, ozone depletion potential and global potential warming value are solved, and meanwhile, the composite polyether has better storage stability. The polyurethane foam prepared by the method for preparing the polyurethane foam by using the combined polyether and the isocyanate is used for heat preservation of a refrigerator and a refrigerator/freezer, and has the advantages of low heat conductivity coefficient, zero ozone consumption potential, environmental friendliness and no pollution.

Description

Polyether for heat preservation of refrigerator/freezer and method for preparing polyurethane rigid foam by using polyether

Technical Field

The invention belongs to the technical field of heat-insulating materials, and relates to composite polyether for heat insulation of a refrigerator/freezer and a method for preparing polyurethane rigid foam by using the composite polyether.

Background

The polyurethane rigid foam plastic is used as a heat insulation material with excellent performance, and is widely applied to the fields of building heat insulation, electrical equipment and the like. However, as people pay more attention to environmental protection, the influence of the foaming agent for preparing the polyurethane rigid foam plastic on the environment is more and more concerned. Blowing agents often destroy the ozone layer and contribute to potential global warming, and to measure the environmental impact of these blowing agents, ODP (ozone depletion potential) and GWP (global warming potential) are measured, respectively.

The physical foaming agent is an essential important component in the production of polyurethane rigid foam plastic (PUR rigid foam for short) for refrigerators, refrigerators and freezers, has a decisive effect on the heat conductivity of the PUR rigid foam, and can influence the foaming process performance and the physical performance of foam.

According to the requirements of Montreal protocol, the second generation foaming agent HCFC-141b is about to be completely eliminated in China. Third generation blowing agents such as HFC-245fa and HFC-365mfc have been banned from use in parts of Europe, japan and the United states. Although the pentane foaming agent is an environment-friendly polyurethane foaming agent which can be permanently used, the pentane foaming agent is inflammable and explosive, has high danger in production operation, has high requirements on equipment and plants, and simultaneously, the foam produced by the pentane foaming agent has high heat conductivity and poor flame retardant property.

The Soltest LBA (HFO-1233 zd) from Honeywell corporation is currently the only commercially available fourth generation blowing agent in large quantities. Although the heat conductivity coefficient (K value) of the PUR rigid foam produced by the foaming agent is superior to that of a third-generation foaming agent such as HCFC-245fa, the polyurethane composite material produced by the foaming agent has poor storage stability and strong corrosivity to plastic liners (ABS or HIPS) commonly used in refrigerators/freezers, a special amine catalyst and a specially developed liner material are required to be used, and the flowability and the mechanical strength of the foam are also reduced.

Disclosure of Invention

The invention provides a combined polyether for heat preservation of a refrigerator/a freezer and a method for preparing polyurethane rigid foam by using the combined polyether, which solve the problem that a polyurethane combined material produced by a foaming agent composition in the prior art is still not ideal in heat conductivity coefficient, ozone depletion potential and global potential warming value.

The technical scheme of the invention is realized as follows:

the combined polyether for the heat preservation of the refrigerator/freezer comprises, by weight, 40-75 parts of high-functionality polyether, 10-40 parts of amino polyether, 0-20 parts of polyol, 1-3.5 parts of silicone surfactant, 1.2-3.2 parts of water, 3-30 parts of cis-1-chloro-2-, 3-tetrafluoropropene, 0-15 parts of C4-C5 hydrocarbon foaming agent and 1.5-5 parts of catalyst.

Further, the high functionality polyether is selected from polyoxypropylene polyols having a hydroxyl number of 360-480 and a functionality of 4 or more.

Further, the polyoxypropylene polyol is prepared from one or more of sucrose, sorbitol, glycerol, propylene glycol or diethylene glycol as a starting agent.

Further, the amino polyether is selected from polyether polyol prepared by taking one or more of toluene diamine, polyaminopolyphenyl methane, o-phenylenediamine, ethylenediamine, diethanolamine or triethanolamine as a starter, and the hydroxyl value of the amino polyether is 350-450.

Further, the polyol includes an aromatic polyester polyol and/or a polyether polyol.

Further, the hydroxyl value of the aromatic polyester polyol is 200-400, and the functionality of the polyether polyol is 2-3; viscosity of no more than 1500mPa.s at 25 ℃.

Further, the silicone surfactant is polyether modified dimethyl siloxane;

is selected from one or more of L-6900, L-6863 of Majiu, B-8465, B-8491, AK-8805 of Maillard, surfactant SH-193, and AK-8830.

Further, the C4-C5 hydrocarbon foaming agent is selected from one or a mixture of more of n-butane, isobutane, cyclopentane, n-pentane and isopentane.

Further, the catalyst is selected from one or a mixture of several of N, N, N, N, N-pentamethyl diethylene triamine, N, N-dimethyl cyclohexylamine, N, N-dimethyl benzylamine, tris (dimethylaminopropyl) hexahydrotriazine, PUCAT 15G (K15%), 2-hydroxy-N, N, N-trimethyl-1-propylamine formate.

A method for preparing polyurethane rigid foam by using combined polyether for heat preservation of a refrigerator/freezer comprises the following steps:

A. preparing a combined polyether: 40-75 parts of high-functionality polyether, 10-40 parts of amino polyether, 0-20 parts of polyol, 1-3.5 parts of organic silicon surfactant, 1.2-3.2 parts of water, 3-30 parts of cis-1-chloro-2-, 3-tetrafluoropropene (HFO-1224 yd), 0-15 parts of C4-C5 hydrocarbon foaming agent and 1.5-5 parts of catalyst; 120-160 parts of isocyanate;

B. mixing high-functionality polyether, amino polyether, polyol, an organosilicon surfactant and water to obtain combined polyether I; mixing cis-1-chloro-2-, 3-tetrafluoropropene and C4-C5 hydrocarbon foaming agents with the combined polyether I to obtain premixed foaming agent combined polyether II; and mixing the premixed foaming agent composite polyether II with isocyanate, injecting the mixture into a film cavity, foaming and curing to obtain the polyurethane rigid foam.

The working principle and the beneficial effects of the invention are as follows:

1. according to the invention, through the proportioning optimization design of the combined polyether, the problems that the heat conductivity coefficient, the ozone depletion potential and the global potential warming value of the polyurethane combined material produced by the foaming agent composition in the prior art are still not ideal are solved, and the combined polyether has better storage stability.

The invention also provides a method for preparing polyurethane foam by utilizing the combined polyether and isocyanate, and the prepared polyurethane foam is used for heat preservation of refrigerators and refrigerators/freezers, and has the advantages of low heat conductivity coefficient, zero ozone consumption potential, environmental friendliness and no pollution.

2. Cis-1-chloro-2-, 3-tetrafluoropropene (HFO-1224 yd) in the invention is a novel fourth-generation non-flammable high-performance environment-friendly foaming agent, which has lower (better) gas-phase thermal conductivity coefficient, gives better heat retaining property, fluidity and dimensional stability to foam, and simultaneously leads the storage stability in polyether of the premixed foaming agent composition to be obviously improved.

Drawings

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

FIG. 1 is a graph showing the results of comparative studies on shelf stability of example 4 of the present invention and comparative experiment 1 and comparative experiment 2;

in the figure, AMOLEA ^TM 1224yd denotes the experimental results of example 4;

HFO-1233zd (E) represents the experimental results of comparative experiment 1;

HFC-245fa/365mfc (70/30 wt%) represents the results of comparative experiment 2.

FIG. 2 is a graph showing the results of comparative studies on shelf stability of example 5 and comparative experiment 3, comparative experiment 4 and comparative experiment 5;

in the figure, AMOLEA ^TM 1224yd denotes the results of the experiment of example 5;

HFO-1233zd (E) represents the experimental results of comparative experiment 3;

HFO-1336mzz (Z) represents the experimental result of comparative experiment 4;

HFC-245fa/365mfc (70/30 wt%) represents the results of comparative experiment 5;

1 denotes AMOLEA ^TM 1224yd；

2 is HFO-1336mzz (Z);

3 represents HFO-1233zd (E);

4 represents HFC-245fa/365mfc (70/30% by weight).

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The following terms used in the present invention have the following definitions or explanations.

The heat conductivity coefficient refers to the heat transferred by a material with unit thickness in a unit temperature difference and time within a 1 square meter area under the condition of stable heat transfer;

the core density refers to the foam center density tested under the condition of excessive filling in a mould used in the manufacturing process of the polyurethane composite board, namely the density of the molded foam core;

pbw refers to the mass parts of each component of the polyurethane reaction system;

functionality, means according to the industry formula: functionality = hydroxyl value (mw) value measured per 56100; wherein the molecular weight is determined by GPC high performance liquid chromatography;

the high functionality polyethers employed in the examples below are selected from polyoxypropylene polyols having a hydroxyl number of 360-480 and a functionality of 4 or greater; the hydroxyl value of the amino polyether is 350-450; the hydroxyl value of the aromatic polyester polyol is 200-400, and the functionality of the polyether polyol is 2-3; viscosity of no more than 1500mPa.s at 25 ℃; the surfactant in the following examples is selected from one or more of L-6900, L-6863, B-8465, B-8491, AK-8805, SH-193, and AK-8830; the C4-C5 hydrocarbon foaming agent is selected from one or a mixture of more of n-butane, isobutane, cyclopentane, n-pentane and isopentane; the catalyst is selected from one or a mixture of more of N, N, N, N, N-pentamethyl diethylene triamine, N, N-dimethyl cyclohexylamine, N, N-dimethyl benzylamine, tri (dimethylaminopropyl) hexahydrotriazine, PUCAT 15G (K15 percent) and 2-hydroxy-N, N, N-trimethyl-1-propylamine formate.

The foaming agent adopted by the invention has the material compatibility performance parameters shown in the following tables 1-2, and the physical property parameters shown in the following table 3.

TABLE 1

TABLE 2

TABLE 3

Example 1

The composite polyether for the heat preservation of the refrigerator/freezer comprises, by weight, 40 parts of high-functionality polyether, 40 parts of aminopolyether, 3.5 parts of silicone surfactant, 1.2 parts of water, 30 parts of cis-1-chloro-2-, 3-tetrafluoropropene and 5 parts of catalyst.

Wherein the high-functionality polyether is prepared by taking sucrose and sorbitol as initiators; the amino polyether is selected from polyether polyol prepared by taking toluenediamine as an initiator, the organosilicon surfactant is surfactant SH-193, and the catalyst is PUCAT 15G (K15%).

A. preparing combined polyether according to the parts by weight; 140 parts of isocyanate;

B. mixing high-functionality polyether, amino polyether, polyol, an organic silicon surfactant and water to obtain combined polyether I; mixing cis-1-chloro-2-, 3-tetrafluoropropene with composite polyether I to obtain premixed foaming agent composite polyether II; and mixing the premixed foaming agent composite polyether II with isocyanate, injecting the mixture into a film cavity, foaming and curing to obtain the polyurethane rigid foam.

Example 2

The composite polyether for the heat preservation of the refrigerator/freezer comprises, by weight, 75 parts of high-functionality polyether, 10 parts of aminopolyether, 20 parts of polyol, 1 part of silicone surfactant, 3.2 parts of water, 3 parts of cis-1-chloro-2-, 3-tetrafluoropropene, 15 parts of C4-C5 hydrocarbon foaming agent and 1.5 parts of catalyst.

Wherein the high-functionality polyether is prepared by taking sucrose, propylene glycol and diethylene glycol as initiators; the amino polyether is selected from polyether polyol prepared by taking ethylene diamine and triethanolamine as an initiator; the polyols include aromatic polyester polyols and polyether polyols; the surfactant is selected from the mixture of L-6900 and L-6863 of Ma picture; the C4-C5 hydrocarbon foaming agent is selected from a mixture of n-butane, isobutane, cyclopentane, n-pentane and isopentane; the catalyst is selected from the group consisting of a mixture of N, N, N, N, N-pentamethyldiethylenetriamine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate.

A. preparing combined polyether according to the parts by weight; 160 parts of isocyanate;

B. mixing high-functionality polyether, amino polyether, polyol, an organic silicon surfactant and water to obtain combined polyether I; mixing cis-1-chloro-2-, 3-tetrafluoropropene and C4-C5 hydrocarbon foaming agents with the composite polyether I to obtain a premixed foaming agent composite polyether II; and mixing the premixed foaming agent composite polyether II with isocyanate, injecting the mixture into a film cavity, foaming and curing to obtain the polyurethane rigid foam.

Example 3

The combined polyether for the heat preservation of the refrigerator/freezer comprises, by weight, 55 parts of high-functionality polyether, 25 parts of amino polyether, 18 parts of polyol, 2 parts of silicone surfactant, 2 parts of water, 24 parts of cis-1-chloro-2-, 3-tetrafluoropropene, 8 parts of C4-C5 hydrocarbon foaming agent and 3.5 parts of catalyst.

Wherein the high-functionality polyether is prepared by taking sucrose and glycerol as initiators; the amino polyether is selected from polyether polyol prepared by taking toluene diamine and triethanolamine as initiators; the polyols include aromatic polyester polyols; the surfactant is selected from mixture of Yingchuang B-8465, B-8491, maillard AK-8805, and AK-8830; the C4-C5 hydrocarbon foaming agent is selected from a mixture of isobutane, cyclopentane and n-pentane; the catalyst is selected from the mixture of N, N-dimethyl cyclohexylamine, N, N-dimethyl benzylamine, tris (dimethylaminopropyl) hexahydrotriazine and 2-hydroxy-N, N, N-trimethyl-1-propylamine formate.

A. preparing combined polyether according to the parts by weight; 120 parts of isocyanate;

B. mixing high-functionality polyether, amino polyether, polyol, an organosilicon surfactant and water to obtain combined polyether I; mixing cis-1-chloro-2-, 3-tetrafluoropropene and C4-C5 hydrocarbon foaming agents with the composite polyether I to obtain a premixed foaming agent composite polyether II; and mixing the premixed foaming agent composite polyether II with isocyanate, injecting the mixture into a film cavity, foaming and curing to obtain the polyurethane rigid foam.

Example 4

The formulation is shown in Table 4, and the process for preparing rigid polyurethane foams is the same as in example 1.

TABLE 4

The indices in table 4 refer to the ratio of polyether polyol to black material.

Example 5

The blowing agent type used was cis-1-chloro-2-, 3-tetrafluoropropene, and the remaining formulations are shown in Table 5.

Example 6

Example 6 the compounding ratio of the conjugate polyether was the same as in example 1, and the amounts of the blowing agent, polycyclic polyisochlorate and conjugate polyether were as shown in table 6 below.

Example 7

The only difference compared to example 2 is that the catalyst was N, N-pentamethyldiethylenetriamine.

Example 8

The only difference compared to example 2 was that the catalyst was 2-hydroxy-N, N, N-trimethyl-1-propylamine formate.

Simultaneously, comparative experiment 1 was set up: the only difference compared to example 4 is that the blowing agent is HFO-1233zd (E).

Set up comparative experiment 2: the only difference compared to example 4 is that the blowing agent is HFC-245fa/365mfc (70/30 wt%).

Comparative experiment 3 used HFO-1233zd (E) and the remaining formulations are shown in Table 5.

Comparative experiment 4 used HFO-1336mzz (Z), and the remaining formulations are shown in Table 5.

Comparative experiment 5 used HFC-245fa/365mfc (70/30 wt%), the rest of the formulation is shown in Table 5.

In comparative experiment 6, comparative experiment 7 and comparative experiment 8, cyclopentane, HSFC 245fa and Solstatic LBA (HFO-1233 zd) were used respectively, the compounding ratio of the composite polyether was the same as that in example 1, and the amounts of the blowing agent, the polycyclic polyisochlorate and the composite polyether were as shown in Table 5 below.

TABLE 5

1. Comparative shelf stability studies were performed on example 4 and

comparative experiments

1 and 2, with manual stirring foaming, under stirring conditions: 3000rpm 5sec, component temperature: 15 degrees celsius. The results are shown in FIG. 1.

2. Example 5 and comparative experiments 3-5 were foamed by hand stirring under the following conditions: 3000rpm 5sec, component temperature: the results of the foam density comparison at 15 degrees celsius are shown in table 6.

TABLE 6

The indices in table 5 refer to the ratio of polyether polyol to black; c.t.s means elicitation time, g.t.s means milky gelation time, r.t.s means tack free time.

3. Comparative shelf stability studies were performed on example 5 and comparative experiment 3, comparative experiment 4, comparative experiment 5, thermal conductivity measurements, sample size: 200X 25mm, conditions: average temperature: 10 ℃ according to EN 12667. The results are shown in FIG. 2.

4. The environmental impact of cis-1-chloro-2-, 3,3,3-tetrafluoropropene, HFO-1233zd (E), HFO-1336mzz (Z), HFC-245fa is shown in Table 7.

TABLE 7

5. The premixed blowing agent of example 1, polyether conjugate II, was tested for storage stability and is designated test A; and the premixed blowing agent polyether II prepared by using the combination of the Honeyvir LBA (HFO-1233 zd) instead of the HFO-1224yd is subjected to a storage stability test, which is recorded as a test B, and the result is shown in the following table 8.

TABLE 8

6. The polyurethane foams prepared in example 4, example 7 and example 8 were tested according to GB/T8811-2008 using a GDJS-010 type constant temperature and humidity test chamber to measure the dimensional change of the foam after 24 hours at a low temperature of-30 ℃ and 24 hours at a high temperature and high humidity condition of 60 ℃ and a relative humidity of 95%, in units%, as shown in Table 9 below.

TABLE 9

Dimensional stability	Example 4	Example 7	Practice ofExample 8
				-30℃	0.4	0.8	0.9
60℃、95％	0.7	1.1	1.2

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The composite polyether for the heat preservation of the refrigerator/freezer is characterized by comprising 40 parts of high-functionality polyether, 40 parts of amino polyether, 3.5 parts of silicone surfactant, 1.2 parts of water, 30 parts of cis-1-chloro-2-, 3-tetrafluoropropene and 5 parts of catalyst in parts by weight;

the high-functionality polyether is polypropylene oxide polyalcohol, the hydroxyl value is 360-480, and the functionality is more than or equal to 4; the hydroxyl value of the amino polyether is 350-450;

wherein the high-functionality polyether is prepared by taking sucrose and sorbitol as initiators; the amino polyether is selected from polyether polyol prepared by taking toluene diamine as an initiator;

the silicone surfactant was surfactant SH-193 and the catalyst was PUCAT 15G, i.e., K15.

2. The method for preparing the rigid polyurethane foam from the combined polyether for the insulation of the refrigerator/freezer as claimed in claim 1, which comprises the following steps:

A. preparing a combined polyether: 40 parts of high-functionality polyether, 40 parts of amino polyether, 3.5 parts of organic silicon surfactant, 1.2 parts of water, 30 parts of cis-1-chloro-2-, 3-tetrafluoropropene and 5 parts of catalyst; 140 parts of isocyanate;

B. mixing high-functionality polyether, amino polyether, polyol, an organosilicon surfactant and water to obtain combined polyether I; mixing cis-1-chloro-2-, 3-tetrafluoropropene with composite polyether I to obtain premixed foaming agent composite polyether II; and mixing the premixed foaming agent composite polyether II with isocyanate, injecting the mixture into a film cavity, foaming and curing to obtain the polyurethane rigid foam.