阅读说明：本技术 一种聚氨酯发泡料及其发泡工艺 (Polyurethane foaming material and foaming process thereof ) 是由 刘鹏 吴园 余泳 江峰 于 2021-08-17 设计创作，主要内容包括：本发明公开了一种聚氨酯发泡料及其发泡工艺,属于家用电器生产领域。本发明包括白料及黑料；白料与黑料之间的比例为1.10-1.40；白料由以下重量份的原料制成：纯白料100份、常温发泡剂6-15份以及高保温发泡剂2-8份；黑料由以下重量份的原料制成：异氰酸酯100份、发泡助剂1-5份以及超低沸点发泡剂1-5份。本发明在不影响聚氨酯泡沫的气泡及保温性能的前提下,通过提高聚氨酯泡沫的物理性能来降低泡沫密度,进而降低发泡原料的灌注量,从而达到节约成本的目标。(The invention discloses a polyurethane foaming material and a foaming process thereof, and belongs to the field of production of household appliances. The invention comprises white material and black material; the ratio of the white material to the black material is 1.10-1.40; the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 6-15 parts of normal-temperature foaming agent and 2-8 parts of high-heat-preservation foaming agent; the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate, 1-5 parts of foaming auxiliary agent and 1-5 parts of ultra-low boiling point foaming agent. According to the invention, on the premise of not influencing the bubbles and the heat preservation performance of the polyurethane foam, the foam density is reduced by improving the physical performance of the polyurethane foam, and the pouring amount of foaming raw materials is further reduced, so that the aim of saving the cost is achieved.)

1. A polyurethane foaming material is characterized by comprising a white material and a black material; the ratio of the white material to the black material is 1.10-1.40;

the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 6-15 parts of normal-temperature foaming agent and 2-8 parts of high-heat-preservation foaming agent;

the pure white material comprises the following raw materials in percentage by mass: 94 to 98 percent of composite polyether, 0.5 to 2.5 percent of surfactant, 1.0 to 2.5 percent of water and 0.5 to 2.5 percent of catalyst;

the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate, 1-5 parts of foaming auxiliary agent and 1-5 parts of ultra-low boiling point foaming agent.

2. The polyurethane foam material as claimed in claim 1, wherein the combined polyether is composed of the following raw materials in mass ratio: 20-65% of sucrose, 15-45% of sorbitol, 15-35% of xylitol, 10-30% of tris (2-hydroxyethyl) isocyanurate and 5-20% of pentaerythritol.

3. The polyurethane foam according to claim 1 or 2, wherein the catalyst comprises the following raw materials in mass ratio: 20% -60% of triethylene diamine, 20% -45% of N, N-dimethyl cyclohexylamine and 20% -40% of dimethyl glycol amine.

4. The polyurethane foam material as claimed in claim 3, wherein the surfactant is composed of the following raw materials in mass ratio: 30% -70% of B-8462 and 30% -70% of L-3001.

5. A polyurethane foam according to claim 1 or 4, wherein said blowing agent at ambient temperature is cyclopentane.

6. The polyurethane foam according to claim 5, wherein the high thermal insulation foaming agent is one or more of LBA, 245fa and FEA-1100.

7. The polyurethane foam according to claim 1, wherein the isocyanate is polymethylene polyphenyl polyisocyanate having an isocyanate group (-NCO group) content of 30% to 35%.

8. A polyurethane foam according to claim 1 or 7, wherein the foaming aid is one or more of C5-18, CZ95190 and PF-5056.

9. The polyurethane foam of claim 8, wherein the ultra low boiling point blowing agent is one or more of butane, 134a, 152a, and GBA.

10. A process for foaming a polyurethane foam according to any one of claims 1 to 9, comprising the steps of:

firstly, premixing combined polyether, water, a surfactant and a catalyst according to a ratio at a material temperature of 20 ℃ to obtain a pure white material; premixing a pure white material, a normal-temperature foaming agent and a high-heat-preservation foaming agent according to a ratio to obtain a white material;

step two, premixing isocyanate, a foaming auxiliary agent and an ultra-low boiling point foaming agent according to a ratio at the material temperature of 20 ℃ to obtain a black material;

step three, injecting white materials and black materials into an inner cavity of a material injection gun head at high speed and high pressure at the same time according to a proportion, fully mixing, and injecting into a to-be-foamed mold through a gun head nozzle;

and step four, after the foaming raw materials are cured in a mold for a period of time, demolding to obtain the hard polyurethane foam heat-insulating layer.

Technical Field

The invention belongs to the field of production of household appliances, and particularly relates to a polyurethane foam material and a foaming process thereof.

Background

In recent years, the reaction speed of a polyurethane foaming system is continuously accelerated in the industry to improve the foaming efficiency and the physical properties of foam, so that the aims of reducing the raw material pouring amount and reducing the foaming cost are fulfilled. In order to improve the foaming efficiency and reduce the foaming cost at the same time, the foaming agent with an ultra-low boiling point (the boiling point is below zero) is added and mixed for use in the industry, and because the boiling point is ultra-low, the foaming agent is gasified more quickly, so that the polyurethane foaming speed is accelerated, and the foaming efficiency is improved; the foaming agent has an ultra-low boiling point, and has high saturated vapor pressure after forming polyurethane foam, so that the foaming agent has high physical properties (such as compression strength and dimensional stability), and further, the material injection amount can be reduced, and the foaming cost can be reduced. However, the addition of an ultra-low boiling point blowing agent brings about the following disadvantages and countermeasures: 1) the ultra-low boiling point foaming agent has large gas phase thermal conductivity, such as 1,1,1, 2-tetrafluoroethane (134 a for short), 1, 1-difluoroethane (152 a for short), butane and trans-1, 3,3, 3-tetrafluoropropene (GBA for short), which are not beneficial to the heat preservation performance. The problem of poor thermal insulation performance can be solved by increasing the foaming agent with high thermal insulation performance or increasing the proportion of the foaming agent with high thermal insulation performance, such as trans-1-chloro-3, 3, 3-trifluoropropene (LBA for short), 1,1,1,3, 3-pentafluoropropane (245 fa for short), and 1,1,1,4,4, 4-hexafluorobutene (FEA-1100 for short). 2) The ultra-low boiling point blowing agents start up particularly quickly, resulting in increased foaming of the foam. The solution is that firstly, better surface active agent is adopted to reduce bubbles generated by foaming and rolling, and secondly, a slower foaming catalyst is adopted to delay the starting speed.

Due to the use of ultra low boiling blowing agents and the addition of LBA/245fa/FEA-1100 blowing agents, these blowing agents have boiling points much lower than the boiling points of the commonly used pentane blowing agents, but the problem of poor bubble formation is not completely solved with the above solutions. In addition to the problem of bubble degradation, other limiting factors exist for ultra low boiling blowing agent systems. The industrial general purpose is that all foaming agents and combined polyether are premixed to prepare white materials, and the premixed white materials and black materials (isocyanate) are foamed through a high-pressure foaming machine at the temperature of 18-22 ℃. As the ultra-low temperature foaming agent system adds more foaming agent (for reasons of defects and solution 1), the solubility of the foaming agent and the conjugate polyether is limited, and the ultra-low boiling point is easier to escape. The temperature of the white material needs to be controlled to be reduced, however, the viscosity of the white material is increased by reducing the temperature of the white material, and the premixing effect of the black and white materials in the injection gun head of the high-pressure foaming machine is influenced. Meanwhile, the white material control temperature is reduced, the application of high-viscosity polyether polyol with high physical strength, high functionality and low thermal conductivity in a foaming system is further limited, and the use of the foaming agent with ultralow boiling point is also limited. Therefore, a polyurethane foam and a foaming process thereof are needed to solve the above problems.

Disclosure of Invention

The invention aims to provide a polyurethane foaming material and a foaming process thereof, and solves the technical problems in the background technology.

In order to solve the technical problems, the invention is realized by the following technical scheme:

the invention relates to a polyurethane foaming material and a foaming process thereof, which comprises a white material and a black material; the ratio of the white material to the black material is 1.10-1.40; the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 6-15 parts of normal-temperature foaming agent and 2-8 parts of high-heat-preservation foaming agent; the pure white material comprises the following raw materials in percentage by mass: 94 to 98 percent of composite polyether, 0.5 to 2.5 percent of surfactant, 1.0 to 2.5 percent of water and 0.5 to 2.5 percent of catalyst; the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate, 1-5 parts of foaming auxiliary agent and 1-5 parts of ultra-low boiling point foaming agent.

Further, the combined polyether is prepared from the following raw materials in percentage by mass: 20-65% of sucrose, 15-45% of sorbitol, 15-35% of xylitol, 10-30% of tris (2-hydroxyethyl) isocyanurate and 5-20% of pentaerythritol.

Further, the catalyst comprises the following raw materials in percentage by mass: 20% -60% of triethylene diamine, 20% -45% of N, N-dimethyl cyclohexylamine and 20% -40% of dimethyl glycol amine.

Further, the surfactant is prepared from the following raw materials in percentage by mass: 30% -70% of B-8462 and 30% -70% of L-3001.

Further, the normal-temperature foaming agent is cyclopentane.

Further, the high-heat-preservation foaming agent is one or more of LBA, 245fa and FEA-1100.

Further, the isocyanate is polymethylene polyphenyl polyisocyanate with the content of isocyanate group (-NCO group) of 30-35%.

Further, the foaming auxiliary agent is one or more of C5-18, CZ95190 and PF-5056.

Further, the ultra low boiling blowing agent is one or more of butane, 134a, 152a, and GBA.

A foaming process of the polyurethane foaming material comprises the following steps:

firstly, premixing combined polyether, water, a surfactant and a catalyst according to a ratio at a material temperature of 20 ℃ to obtain a pure white material; premixing a pure white material, a normal-temperature foaming agent and a high-heat-preservation foaming agent according to a ratio to obtain a white material;

step two, premixing isocyanate, a foaming auxiliary agent and an ultra-low boiling point foaming agent according to a ratio at the material temperature of 20 ℃ to obtain a black material;

step three, injecting white materials and black materials into an inner cavity of a material injection gun head at high speed and high pressure at the same time according to a proportion, fully mixing, and injecting into a to-be-foamed mold through a gun head nozzle;

and step four, after the foaming raw materials are cured in a mold for a period of time, demolding to obtain the hard polyurethane foam heat-insulating layer.

The invention has the following beneficial effects:

1. on the premise of not influencing bubbles, the invention improves the foaming production efficiency, reduces the foaming cost, avoids reducing the white material control temperature, breaks through the limitation of high-viscosity polyether polyol with high physical strength, high functionality and low heat conductivity, and cancels the limitation of the part of foaming agent with ultra-low boiling point.

2. The invention optimizes the premixing mode of foaming raw materials, fully exerts the advantages of the designed foaming system, and is beneficial to improving the part of the low-boiling-point foaming agent, thereby greatly reducing the core density.

3. Compared with an ultralow-boiling-point foaming system in the prior art, the foaming system has higher foaming quality and reduces the problem of bubbles; meanwhile, compared with the material temperature control system of the existing foaming system, the material temperature control difficulty is reduced, the foaming reaction speed is accelerated, and the foaming efficiency is improved.

Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 invention relates to a polyurethane foaming material, which comprises a white material and a black material; the ratio of the white material to the black material is 1.10-1.40;

the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 6-15 parts of normal-temperature foaming agent and 2-8 parts of high-heat-preservation foaming agent; the pure white material comprises the following raw materials in percentage by mass: 94 to 98 percent of composite polyether, 0.5 to 2.5 percent of surfactant, 1.0 to 2.5 percent of water and 0.5 to 2.5 percent of catalyst; the composite polyether is prepared from the following raw materials in percentage by mass: 20% -65% of sucrose, 15% -45% of sorbitol, 15% -35% of xylitol, 10% -30% of tris (2-hydroxyethyl) isocyanurate and 5% -20% of pentaerythritol; the catalyst comprises the following raw materials in percentage by mass: 20% -60% of triethylene diamine, 20% -45% of N, N-dimethyl cyclohexylamine and 20% -40% of dimethyl glycol amine; the surfactant is prepared from the following raw materials in percentage by mass: 30% -70% of brand B-8462 (manufactured by Gauss Miller Co., Ltd.) and 30% -70% of brand L-3001 (manufactured by Witco, USA); the normal-temperature foaming agent is cyclopentane; the high-heat-preservation foaming agent is one or more of LBA, 245fa and FEA-1100;

the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate, 1-5 parts of foaming auxiliary agent and 1-5 parts of ultra-low boiling point foaming agent; the isocyanate is polymethylene polyphenyl polyisocyanate with the content of isocyanate group (-NCO group) of 30-35 percent, the industry is called polymeric MDI, and the isocyanate is provided by Wanhua chemical group Limited company and has the mark of PM-200; the foaming auxiliary agent is one or more of C5-18 (perfluoroolefin compound provided by Hongbaoli group company, chemical substance number is CAS number: 86508-42-1), CZ95190 (perfluoroolefin compound provided by BASF polyurethane (China) Co., Ltd., chemical substance number is CAS number: 84650-68-0) and PF-5056 (mixture of 60-90% perfluoromorpholine and 10-40% perfluoroalkane provided by 3M (China) Co., Ltd.); the ultra-low boiling blowing agent is one or more of butane, 134a, 152a, and GBA.

A foaming process of the polyurethane foaming material comprises the following steps:

firstly, premixing combined polyether, water, a surfactant and a catalyst according to a ratio at a material temperature of 20 ℃ to obtain a pure white material; premixing a pure white material, a normal-temperature foaming agent and a high-heat-preservation foaming agent according to a ratio to obtain a white material;

step two, premixing isocyanate, a foaming auxiliary agent and an ultra-low boiling point foaming agent according to a ratio at the material temperature of 20 ℃ to obtain a black material;

step three, injecting white materials and black materials into an inner cavity of a material injection gun head at high speed and high pressure at the same time according to a proportion, fully mixing, and injecting into a to-be-foamed mold through a gun head nozzle;

and step four, after the foaming raw materials are cured in a mold for a period of time, demolding to obtain the hard polyurethane foam heat-insulating layer.

Example 1:

the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 10 parts of normal-temperature foaming agent and 4 parts of high-heat-preservation foaming agent;

the pure white material comprises the following raw materials in percentage by mass: 95% of combined polyether, 1.5% of surfactant, 15% of water and 2.0% of catalyst;

the composite polyether is prepared from the following raw materials in percentage by mass: 45% sucrose, 20% sorbitol, 10% xylitol, 15% tris (2-hydroxyethyl) isocyanurate and 10% pentaerythritol;

the catalyst comprises the following raw materials in percentage by mass: 40% triethylenediamine, 35% N, N-dimethylcyclohexylamine and 25% dimethylethyleneglycol amine;

the surfactant is prepared from the following raw materials in percentage by mass: 60% brand B-8462 (manufactured by Gauss Mills) and 40% brand L-3001 (manufactured by Witco, USA);

the normal-temperature foaming agent is cyclopentane;

the high-heat-preservation foaming agent is LBA;

the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate, 2 parts of foaming auxiliary agent and 2 parts of ultra-low boiling point foaming agent;

the isocyanate is polymethylene polyphenyl polyisocyanate with the content of isocyanate group (-NCO group) of 30-35 percent, the industry is called polymeric MDI, and the isocyanate is provided by Wanhua chemical group Limited company and has the mark of PM-200;

the foaming auxiliary agent is C5-18 (perfluoroolefin compound provided by Hongbaoli group company, chemical substance number is CAS number 86508-42-1);

the ultra-low boiling point foaming agent is 134 a;

the ratio of white material to black material is 1.20.

Example 2:

the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 10 parts of normal-temperature foaming agent and 7 parts of high-heat-preservation foaming agent;

the pure white material comprises the following raw materials in percentage by mass: 95% of combined polyether, 1.5% of surfactant, 1.5% of water and 2.0% of catalyst;

the composite polyether is prepared from the following raw materials in percentage by mass: 45% sucrose, 20% sorbitol, 10% xylitol, 15% tris (2-hydroxyethyl) isocyanurate and 10% pentaerythritol;

the catalyst comprises the following raw materials in percentage by mass: 40% triethylenediamine, 35% N, N-dimethylcyclohexylamine and 25% dimethylethyleneglycol amine;

the surfactant is prepared from the following raw materials in percentage by mass: 60% brand B-8462 (manufactured by Gauss Mills) and 40% brand L-3001 (manufactured by Witco, USA);

the normal-temperature foaming agent is cyclopentane;

the high-heat-preservation foaming agent is LBA;

the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate, 2 parts of foaming auxiliary agent and 3 parts of ultra-low boiling point foaming agent;

the isocyanate is polymethylene polyphenyl polyisocyanate with the content of isocyanate group (-NCO group) of 30-35 percent, the industry is called polymeric MDI, and the isocyanate is provided by Wanhua chemical group Limited company and has the mark of PM-200;

the foaming auxiliary agent is C5-18 (perfluoroolefin compound provided by Hongbaoli group company, chemical substance number is CAS number 86508-42-1);

the ultra-low boiling point foaming agent is 134 a;

the ratio of white material to black material is 1.20.

Example 3:

the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 10 parts of normal-temperature foaming agent and 6 parts of high-heat-preservation foaming agent;

the pure white material comprises the following raw materials in percentage by mass: 95% of combined polyether, 1.5% of surfactant, 15% of water and 2.0% of catalyst;

the composite polyether is prepared from the following raw materials in percentage by mass: 45% sucrose, 20% sorbitol, 10% xylitol, 15% tris (2-hydroxyethyl) isocyanurate and 10% pentaerythritol;

the catalyst comprises the following raw materials in percentage by mass: 40% triethylenediamine, 35% N, N-dimethylcyclohexylamine and 25% dimethylethyleneglycol amine;

the surfactant is prepared from the following raw materials in percentage by mass: 60% brand B-8462 (manufactured by Gauss Mills) and 40% brand L-3001 (manufactured by Witco, USA);

the normal-temperature foaming agent is cyclopentane;

the high-heat-preservation foaming agent is LBA;

the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate and 2 parts of an ultra-low boiling point foaming agent;

the isocyanate is polymethylene polyphenyl polyisocyanate with the content of isocyanate group (-NCO group) of 30-35 percent, the industry is called polymeric MDI, and the isocyanate is provided by Wanhua chemical group Limited company and has the mark of PM-200;

the ultra-low boiling point foaming agent is 134 a;

the ratio of white material to black material is 1.20.

Example 4:

the white material is prepared from the following raw materials in parts by weight: 100 parts of pure white material, 10 parts of normal-temperature foaming agent and 9 parts of high-heat-preservation foaming agent;

the pure white material comprises the following raw materials in percentage by mass: 95% of combined polyether, 1.5% of surfactant, 15% of water and 2.0% of catalyst;

the composite polyether is prepared from the following raw materials in percentage by mass: 45% sucrose, 20% sorbitol, 10% xylitol, 15% tris (2-hydroxyethyl) isocyanurate and 10% pentaerythritol;

the catalyst comprises the following raw materials in percentage by mass: 40% triethylenediamine, 35% N, N-dimethylcyclohexylamine and 25% dimethylethyleneglycol amine;

the surfactant is prepared from the following raw materials in percentage by mass: 60% brand B-8462 (manufactured by Gauss Mills) and 40% brand L-3001 (manufactured by Witco, USA);

the normal-temperature foaming agent is cyclopentane;

the high-heat-preservation foaming agent is LBA;

the black material is prepared from the following raw materials in parts by weight: 100 parts of isocyanate and 3 parts of an ultra-low boiling point foaming agent;

the isocyanate is polymethylene polyphenyl polyisocyanate with the content of isocyanate group (-NCO group) of 30-35 percent, the industry is called polymeric MDI, and the isocyanate is provided by Wanhua chemical group Limited company and has the mark of PM-200;

the ultra-low boiling point foaming agent is 134 a;

the ratio of white material to black material is 1.20.

It can be seen that example 1 is mainly different from example 2 in the number of parts of the ultra-low boiling point blowing agent, and is used for verifying the physical properties of the polyurethane foam, i.e., verifying the degree of reducing the foaming cost; meanwhile, the influence of the part of the foaming agent with the ultra-low boiling point on the bubbles is verified; the same applies to example 3 and example 4. The main difference between example 1 and example 3 is whether a perfluoro compound foaming aid is contained or not, and is used for verifying the influence of the foaming aid on bubbles and physical properties; the same applies to example 2 and example 4.

The polyurethane foams obtained from the four foaming systems of example 1, example 2, example 3 and example 4 were tested in comparison, and the technical parameters are shown in the following table:

note: the bubble number judging method comprises the following steps: the bubbles with the diameter less than 1cm are not included, the bubbles with the diameter more than 1cm and less than 2cm are B-type bubbles, the bubbles with the diameter more than 2cm are A-type bubbles, and 1A-type bubble is calculated according to 4B bubbles.

As can be seen by comparing example 1 with example 2 in the table above, the increase of the ultra-low boiling point foaming agent obviously improves the physical properties of the polyurethane foam, such as dimensional stability and compressive strength, which means that the cost reduction space is larger; the reaction speed is increased by adding the foaming agent with the ultralow boiling point, so that the production efficiency is improved; but the increase of bubbles is more pronounced. Meanwhile, the increase of bubbles is more obvious by comparing the example 3 with the example 4. The increase of foaming agents with ultralow boiling points can be obtained, which is beneficial to the improvement of physical properties and foaming efficiency, but causes the increase of foaming and influences the foaming quality.

The comparison between example 1 and example 3 and between example 2 and example 4 shows that the foaming auxiliary agent can improve the heat insulation performance of polyurethane foam; especially, the improvement on the bubbles is obvious, and the number of the bubbles can be reduced. In the actual mass application process, the invention can reduce the waste products caused by the quality problem of the bubbles, reduce the rejection rate of the products and save the production cost.

In summary, the foaming auxiliary can solve or improve the problem of bubbles caused by an ultra-low boiling point foaming system, and the foaming system combining the foaming auxiliary and the ultra-low boiling point foaming agent has the beneficial factors of reducing the foaming cost (improving the physical properties of polyurethane foam and reducing the material injection amount), improving the production efficiency (wire drawing time), improving foam bubbles and the like.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.