阅读说明：本技术 一种管道用喷涂型环保硬质聚氨酯泡沫原料组合物 (Spraying type environment-friendly rigid polyurethane foam raw material composition for pipeline ) 是由 信延垒 任丽 任洁洁 于 2020-12-23 设计创作，主要内容包括：本发明涉及一种管道用喷涂型环保硬质聚氨酯泡沫原料组合物,由组分A和组分B组成,组分A为聚醚多元醇a、聚醚多元醇b、有机硅表面活性剂、催化剂、交联剂、水混合而成；组分B为多苯基多亚甲基多异氰酸酯；组分A和组分B质量比例为100：145-160。本发明采用水作为化学发泡剂,水与异氰酸酯反应生成二氧化碳(CO-2)起到发泡作用,达到真正环保；并通过合理设计配方得到的硬质聚氨酯泡沫具有良好的保温性能和机械性能。(The invention relates to a spraying type environment-friendly rigid polyurethane foam raw material composition for a pipeline, which consists of a component A and a component B, wherein the component A is formed by mixing polyether polyol a, polyether polyol B, an organic silicon surfactant, a catalyst, a cross-linking agent and water; the component B is polyphenyl polymethylene polyisocyanate; the mass ratio of the component A to the component B is 100: 145-160. The invention adopts water as a chemical foaming agent, and the water reacts with isocyanate to generate carbon dioxide (CO) 2 ) Plays a foaming role and achieves real environmental protection; the rigid polyurethane foam obtained by reasonably designing the formula has good heat insulation performance and mechanical performance.)

1. A spraying type environment-friendly rigid polyurethane foam raw material composition for a pipeline is characterized by comprising a component A and a component B, wherein the component A comprises the following components in parts by weight: 60-80 parts of polyether polyol a, 20-40 parts of polyether polyol b, 1-4 parts of organosilicon surfactant, 4-8 parts of catalyst, 1-5 parts of cross-linking agent and 2.0-3.0 parts of water; the catalyst is one or more of low-odor reactive catalysts such as trimethyl hydroxyethyl ethylenediamine Dabco T and PT303, gel catalysts PC77 and triethylene diamine, trimerization catalysts N, N' -tris (dimethylaminopropyl) -hexahydrotriazine, JXP508 and quaternary ammonium salt;

the component B is polyphenyl polymethylene polyisocyanate;

the mass ratio of the component A to the component B is 100: 145-160.

2. The spray type environment-friendly rigid polyurethane foam raw material composition for the pipeline as claimed in claim 1, wherein the catalyst is a composite of a foaming type catalyst Dabco T, a gel type catalyst PC77 and a trimerization type catalyst JXP-508.

3. The spray type environment-friendly rigid polyurethane foam raw material composition for the pipeline as claimed in claim 1, wherein the polyether polyol a is prepared by polymerizing one or more compounds of micromolecular polyol with an active group of at least 2 serving as an initiator with propylene oxide or ethylene oxide, and is terminated by propylene oxide.

4. The sprayable environmental friendly rigid polyurethane foam starting composition of claim 3 wherein the polyether polyol a is polymerized from sorbitol and propylene oxide and capped with propylene oxide.

5. The spray-type environmentally friendly rigid polyurethane foam raw material composition for pipes as claimed in claim 1, wherein the polyether polyol a has a viscosity of 1000-5000mPa.s at 25 ℃, a hydroxyl value of 300-500mgKOH/g and a functionality of 4.0-6.0.

6. The spray type environment-friendly rigid polyurethane foam raw material composition for pipelines as claimed in claim 1, wherein the polyether polyol b is prepared by polymerizing one or more compounds of micromolecular polyol with an active group of at least 2 serving as an initiator with propylene oxide or ethylene oxide and is terminated by propylene oxide.

7. The spray-type environmentally friendly rigid polyurethane foam raw material composition for pipes as claimed in claim 1, wherein the polyether polyol b has a viscosity of 200-400mPa.s at 25 ℃ and a hydroxyl value of 160-500 mgKOH/g.

8. The spray type environment-friendly rigid polyurethane foam raw material composition for pipelines as claimed in claim 1, wherein the crosslinking agent is one or a mixture of glycerol and alcamines.

9. The spray-type environmentally friendly rigid polyurethane foam raw material composition for pipes as claimed in claim 1, wherein the viscosity of the component A is 500-1000mPa.s at 25 ℃.

10. The process for producing a spray type environmentally friendly rigid polyurethane foam for pipes using the composition as claimed in claim 1, characterized by comprising the steps of uniformly mixing the raw materials of component A in a mixing vessel having a safety device and a stirring speed of 500rpm for 0.5 to 1 hour, standing for 0.5 to 1 hour for defoaming, and discharging to obtain component A;

spraying the component A and the component B by a polyurethane spraying machine to prepare hard polyurethane foam; control parameters of the spraying machine are as follows: controlling the heating temperature of the pipeline to be 50 +/-10 ℃, controlling the machine pressure to be 1200-1500psi, and controlling the mass ratio of the component A to the component B to be 100: 145-160.

Technical Field

The invention relates to a spraying type environment-friendly hard polyurethane raw material composition for a pipeline and a using method thereof, belonging to the technical field of chemical synthesis.

Background

Polyurethane heat-insulating pipelines are widely used for steam heating pipelines and petroleum and natural gas conveying pipelines due to excellent heat-insulating performance; with the development of national urbanization and the promotion of the national strategy of oil and gas land pipeline transportation, the demand of polyurethane heat-insulating pipelines is increasing. At present, the manufacturing of polyurethane heat-insulating pipelines is mainly carried out by a 'pouring method' molding process, and foaming raw materials flow along the axial direction for a long distance in the production process, so that the problems of large density gradient of heat-insulating foam of the pipelines, cavities in foam bodies, axial stretching of the foam and the like exist; causes the problems of more raw materials, poor heat insulation performance, low compressive strength, shrinkage and the like of the foam.

In recent two years, the spraying winding pipeline production line is introduced successively by domestic large-scale pipeline production enterprises, the production mode successfully solves the problems existing in the casting method production process, however, the raw material selection faces limitations, the relatively mature spraying type raw material technology is mainly mastered by other enterprises such as Corcission, Hensmei and the like, and the product is relatively high in price. Corresponding research is carried out in domestic enterprises, and patent CN103694435A discloses special environment-friendly combined polyether for spraying type pipelines and a preparation method thereof, HFC-245fa is adopted as a physical foaming agent, HFC-245fa is a high-temperature room gas substance, and the greenhouse effect value is 1030; the foaming agent is a transitional third-generation physical foaming agent, is forbidden to be used in developed countries in Europe and America at present, and is up to 2035 years in the global range; 245 are expensive and costly. However, if no physical foaming agent is used, the physical index of the product is greatly changed, the process usability is deteriorated, and the performance of the rigid polyurethane foam is not easy to reach the technical performance required by national standards. Therefore, the development of the spraying and winding pipeline technology with environmental protection, low cost and good performance can have good application prospect.

Disclosure of Invention

The invention aims to provide a spraying type environment-friendly rigid polyurethane foam raw material composition for a pipeline, which adopts water as a chemical foaming agent, and the water reacts with isocyanate to generate carbon dioxide (CO)₂) Play a role of foaming to achieveThe environment is really protected; the rigid polyurethane foam obtained by reasonably designing the formula has good heat insulation performance and mechanical performance.

The technical scheme adopted by the invention is as follows:

a spraying type environment-friendly rigid polyurethane foam raw material composition for a pipeline comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 60-80 parts of polyether polyol a, 20-40 parts of polyether polyol b, 1-4 parts of organosilicon surfactant, 4-8 parts of catalyst, 1-5 parts of cross-linking agent and 2.0-3.0 parts of water; the catalyst is one or more of low-odor reactive catalysts such as trimethyl hydroxyethyl ethylenediamine Dabco T and PT303, gel catalysts PC77 and triethylene diamine, trimerization catalysts N, N' -tris (dimethylaminopropyl) -hexahydrotriazine, JXP508 and quaternary ammonium salt;

the component B is polyphenyl polymethylene polyisocyanate;

the mass ratio of the component A to the component B is 100: 145-160.

The catalyst is preferably compounded by a foaming catalyst Dabco T, a gel catalyst PC77 and a trimerization catalyst JXP-508; further preferably, the mass ratio of the foaming catalyst Dabco T to the gel catalyst PC77 to the trimerization catalyst JXP-508 is 1: 2: 2.

the polyether polyol a is prepared by polymerizing one or more compounds of micromolecular polyhydric alcohols with at least 2 active groups, such as sucrose, sorbitol, pentaerythritol, ethylenediamine, toluenediamine, glycerol, ethylene glycol, propylene glycol, diethylene glycol and the like, with propylene oxide or ethylene oxide by using an initiator and sealing by using the propylene oxide; preferably sorbitol is polymerized with propylene oxide.

The viscosity of the polyether polyol a is 1000-5000mPa.s (25 ℃), the hydroxyl value is 300-500mgKOH/g, and the functionality is 4.0-6.0; further preferably has a viscosity of 1500-3500mPa.s (25 ℃ C.), a hydroxyl value of 320-400mgKOH/g and a functionality of 4.0-5.0.

The polyether polyol b is prepared by taking one or more compounds of micromolecular polyhydric alcohols with at least 2 active groups such as glycerol, ethylene glycol, propylene glycol, diethylene glycol and the like as an initiator and polymerizing with propylene oxide or ethylene oxide, and is terminated by propylene oxide; preferably glycerol is polymerized with propylene oxide.

The viscosity of the polyether polyol b is 200-400mPa.s (25 ℃), and the hydroxyl value is 160-500 mgKOH/g; further preferably 220-350 mgKOH/g.

The organic silicon surfactant can be selected from S series products of Shanghai Maihao chemical technology, Inc., B series products of Yingchuang group, L series products of Mi chart high-tech materials or AK series products of Jiangsu Meiside chemical corporation, and further preferably selected from S-198 of Shanghai Maihao chemical technology, Inc.

The cross-linking agent is one or a mixture of more of glycerol and alcohol amine substances, and TEA is further preferred.

The water is preferably deionized water.

The viscosity of the component A is 500-1000mPa.s (25 ℃).

A method for preparing a spray type environment-friendly rigid polyurethane foam for pipelines by using the composition comprises the following steps:

uniformly mixing the raw materials of the component A in a mixing kettle with a safety device and a stirring speed of 500rpm for 0.5-1 hour, standing for 0.5-1 hour for defoaming, and discharging to obtain the component A;

spraying the component A and the component B by a polyurethane spraying machine to prepare hard polyurethane foam; control parameters of the spraying machine are as follows: controlling the heating temperature of the pipeline to be 50 +/-10 ℃, controlling the machine pressure to be 1200-1500psi, and controlling the mass ratio of the component A to the component B to be 100: 150-160.

After the spraying type environment-friendly rigid polyurethane foam for the pipeline is cured for 48 hours at normal temperature, various performances are tested.

The invention has the advantages that:

1) water is adopted as a chemical foaming agent, so that real environmental protection is realized, and the cost is reduced by 15-20% compared with physical foaming;

2) the odor and safety problems of the working environment are improved by adopting a low-odor reaction type catalyst; the delayed trimerization catalyst JXP-508 is adopted to solve the problems of foam burning and cracking; the foaming, gelling and trimerization composite catalyst is adopted to balance chemical reaction, so that the foam forming process is more stable, and the complex production process condition is met;

3) the proportion of the component B is improved through the formula design, and the hard polyurethane foam with more excellent compressive strength and high temperature resistance is prepared;

4) the product of the invention can meet the pipeline spraying construction process and solve the problems of large density distribution, cavities in the foam body and low radial compressive strength in the casting molding process.

Detailed Description

In order that the technical features and contents of the present invention can be understood in detail, the present invention is further described with reference to the following embodiments.

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

polyether polyol a: NJ-8268, hydroxyl value 320mgKOH/g, viscosity 1500mPa.s, available from Tanshun Ningwu New Material Co., Ltd;

polyether polyol b: NJ-307, hydroxyl value 250mgKOH/g, viscosity 300mPa.s, available from Tanshun Ningwu New materials Co., Ltd;

foam stabilizer S-198 was purchased from Shanghai Maihao chemical science and technology, Inc.;

catalysts Dabco T, PC77 and JXP-508 were purchased from EVONIK;

crosslinker TEA available from Iavailable Chemicals, Inc.;

self-made deionized water;

polyphenyl polymethylene polyisocyanate: PM200, available from Wanhua Chemicals.

Examples 1 to 3

Preparation of rigid polyurethane foams the formulations of examples 1 to 3 in parts by weight are given in Table 1 below:

TABLE 1

The preparation method comprises the following steps: uniformly mixing the raw materials of the component A in a mixing kettle with a safety device and a stirring speed of 500rpm for 0.8 hour, standing for 1 hour for defoaming, and discharging to obtain the component A;

spraying the component A and the component B by a polyurethane spraying machine to prepare hard polyurethane foam; control parameters of the spraying machine are as follows: controlling the heating temperature of a pipeline to be 50 +/-10 ℃, controlling the pressure of a machine to be 1300psi, and controlling the mass ratio of a component A to a component B of the machine to be 100: 145-160.

Comparative example 1

411045 parts of polyether polyol, 620515 parts of polyether polyol, MN-10007 parts of polyether polyol, PS-31525 parts of polyester polyol, L-69201.5 parts of silicone surfactant, 3031.5 parts of catalyst PT, A-332.7 parts of catalyst PT 3042.0 parts of catalyst T-120.3 parts of foaming agent HFC-245fa 18 parts of polyether polyol, and the component A is prepared by the method of the embodiment;

wherein, the functionality of the polyether polyol 4110 is 4.5, the hydroxyl value is 430mgKOH/g, and the viscosity is 3500 mPa.s;

polyether polyol 6205 has a functionality of 4.0, a hydroxyl value of 380mgKOH/g, and a viscosity of 2500 mPa.s;

the functionality of the polyether polyol MN-1000 is 3.0, the hydroxyl value is 240mgKOH/g, and the viscosity is 300 mPa.s;

the functionality of the polyester polyol PS-3152 is 2.0, the hydroxyl value is 315mgKOH/g, and the viscosity is 2500 mPa.s.

Spraying the component A and the component B by a polyurethane spraying machine to prepare hard polyurethane foam; control parameters of the spraying machine are as follows: controlling the heating temperature of a pipeline to be 50 +/-10 ℃, controlling the pressure of a machine to be 1300psi, and controlling the mass ratio of a component A to a component B of the machine to be 100: 100.

the properties of the rigid polyurethane foams prepared in examples and comparative examples, which were tested after 48 hours of room temperature aging, are as follows:

TABLE 2

Item	Example 1	Example 2	Example 3	Comparative example
					Foam density, kg/m3	63.7	62.5	62.6	63.7
Radial compressive strength, kPa	426	483	448	439
					Closed cell rate,%	95.3	94.7	94.5	92.1
Thermal conductivity, mW/m.k	24.72	25.65	25.07	26.93
					Water absorption percentage%	0.93	0.85	1.02	3.85
Foam cavity	Is free of	Is free of	Is free of	Is free of

The performance of the hard polyurethane foam reaches the technical requirements of 'high-density polyethylene outer protective pipe polyurethane foam prefabricated direct-buried heat-insulation pipe' CJ/T114-2000 standard: the density is more than or equal to 60kg/m³The radial compressive strength is more than or equal to 300kPa, the heat conductivity coefficient is less than or equal to 0.030mW/m.k, the water absorption is less than or equal to 10 percent, and the foam cavity is less than or equal to 1/3.

Tests prove that the rigid polyurethane foam material prepared by the invention can meet the technical requirements of the directly buried pipe. And the comparative example component A is added with 18 percent of physical foaming agent HFC-245fa, and the HFC-245fa has higher greenhouse gas effect and is about 50 yuan/kg expensive, and the cost is increased by 40 percent compared with the embodiment. Even when the foam is prepared by water foaming at the conventional A, B component 100:100 ratio, the performance of the foam cannot reach the standard.

Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.