阅读说明：本技术 戊烷喷涂型聚氨酯组合聚醚及其制备方法 (Pentane spraying type polyurethane combined polyether and preparation method thereof ) 是由 殷晓峰 王树庆 李金伟 李宗儒 于 2020-12-25 设计创作，主要内容包括：本发明涉及一种戊烷喷涂型聚氨酯组合聚醚的制备及其应用方法。本发明所述的戊烷喷涂型聚氨酯组合聚醚,由聚醚多元醇A、聚酯多元醇B、聚醚多元醇C、聚醚多元醇D、催化剂、阻燃剂、泡沫稳定剂、化学发泡剂、戊烷发泡剂组成。该组合聚醚与常规产品相比,解决了喷涂行业的发泡剂替代问题,替代后的阻燃问题与发泡粘度问题,该组合聚醚具有发泡剂环保,无ODS物质的特点,同时产品整体密度与综合成本低于常规141b类产品,产品综合性能满足GB50404-2017性能要求。(The invention relates to a preparation method and an application method of pentane spraying type polyurethane combined polyether. The pentane spraying type polyurethane combined polyether comprises polyether polyol A, polyester polyol B, polyether polyol C, polyether polyol D, a catalyst, a flame retardant, a foam stabilizer, a chemical foaming agent and a pentane foaming agent. Compared with the conventional product, the combined polyether solves the problems of the replacement of a foaming agent, the flame retardance after replacement and the foaming viscosity in the spraying industry, has the characteristics of environmental protection of the foaming agent and no ODS (ozone depleting substance), has lower overall density and comprehensive cost than the conventional 141b product, and meets the performance requirements of GB50404-2017 in terms of the comprehensive performance of the product.)

1. The pentane spraying type polyurethane combined polyether is characterized in that: the composite material is prepared from the following raw materials in parts by weight:

the polyether polyol A is polyether polyol which uses sucrose as one or all of the initiators, has the functionality of 4.5-7.5 and the hydroxyl value of 350-500 mgKOH/g;

the polyether polyol C is polyether polyol which uses ethylenediamine as one or all of the initiators, the functionality is 3.5-4.5, and the hydroxyl value is 700-800 mgKOH/g;

polyether polyol D is a polyether polyol using glycerol as one or all of the initiators, and has a functionality of 2.5 to 3.5 and a hydroxyl value of 150-500 mgKOH/g.

2. The pentane spray polyurethane composite polyether of claim 1, wherein: the polyester polyol B is phthalic anhydride polyester polyol, the functionality is 2-2.5, and the hydroxyl value is 150-350 mgKOH/g.

3. The pentane spray polyurethane composite polyether of claim 1, wherein: the catalyst is a mixture of a tertiary amine hydrolysis-resistant catalyst and an organic metal catalyst.

4. The pentane spray polyurethane conjugate polyether of claim 3, wherein: the catalyst is a mixture of bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine, 33% triethylene diamine solution, tris (dimethylaminopropyl) hexahydrotriazine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate and potassium isooctanoate, and the mixing mass ratio of the two is 1-4.2:1-2.5:1-3.5:1-2.5:0.3-1: 1-3.

5. The pentane spray polyurethane composite polyether of claim 1, wherein: the foam stabilizer is polyether modified organosilicon surfactant.

6. The pentane spray polyurethane composite polyether of claim 1, wherein: the flame retardant is a mixture of TCPP and TEP which are compounded according to the mass ratio of 2.5-5: 1.

7. The pentane spray polyurethane composite polyether of claim 1, wherein: the chemical foaming agent is water; the pentane foaming agent is one or two of cyclopentane and isopentane.

8. The pentane spray polyurethane composite polyether of claim 1, wherein: the mass ratio of the chemical foaming agent to the pentane foaming agent is 1.7-1.9: 4.2-5.7.

9. A method for preparing the pentane spraying type polyurethane combined polyether as described in any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:

sequentially mixing polyether polyol A, polyester polyol B, polyether polyol C, polyether polyol D, a foam stabilizer, a catalyst, a flame retardant, a chemical foaming agent and a pentane foaming agent, and stirring at normal temperature for 0.3-0.5h to obtain the pentane spraying type polyurethane combined polyether.

10. The use of the pentane spray polyurethane conjugate polyether of any one of claims 1-8, wherein: when the component A and the component B are used, the component A and the component B are mixed according to the weight ratio of 100: 100-.

Technical Field

The invention relates to the technical field of polyurethane rigid foam, in particular to pentane spraying type polyurethane combined polyether and a preparation method thereof.

Background

The polyurethane foam is outstanding in all heat insulation materials at present, and is widely applied to heat supply pipelines, petrochemical pipelines, transportation, refrigerators and freezers, building heat preservation, aviation and military and other aspects. The polyurethane spraying product has excellent heat preservation performance because the foaming process is rapid, the foam holes are extremely fine and smooth, the lowest heat conductivity coefficient can reach below 0.020W/m.k (23 ℃), and meanwhile, because the foaming process is carried out by being attached to the base material, the polyurethane spraying product is closely adhered to the base material, the adhesive force is good, and the integral performance with the base material is excellent; in addition, the spraying construction process has simple processing technology and convenient construction, and the polyurethane spraying material has wider and wider application in the aspects of building energy conservation and heat preservation and refrigeration house cold preservation and has wide market prospect.

Currently, monofluorodichloroethane 141b is used as a foaming agent of spray type combined polyether, and the foaming agent has 1/10 of CFC-113 for destroying the ozone layer, but also has certain destruction to the ozone layer, and belongs to ODS substances. Meanwhile, the dimensional stability of the 141b foaming agent is inferior to that of CFC-113, the foaming multiplying power and the physical properties of foam are reduced more, the market price of 141b is about 25000 yuan, and the comprehensive cost is higher. C5 foaming agents such as cyclopentane, n-pentane and isopentane have good foaming effect and no damage to an ozone layer, and are a preferable alternative scheme of the foaming agents in the polyurethane industry, but the foaming agents of the type have poor intersolubility and low flash point, belong to flammable and explosive articles, have large influence on the flame retardant effect of foams after pentane is added into the system, and cannot be used in a spraying system at present.

In recent years, the polyurethane spraying industry develops rapidly, but with the promotion of 141b replacing process, the foaming agent replacement of a spraying system is urgent, if pentane foaming can be used, the problem of system intersolubility is solved, the problem of system flame retardance is solved, the problem of system viscosity is solved, and the pentane spraying type polyurethane material is researched and developed by means of the cost advantage of the pentane foaming agent and the mechanical property characteristics of foam, so that a positive guiding effect can be formed on the polyurethane market.

Disclosure of Invention

The technical problem to be solved by the invention is to provide the pentane spraying type polyurethane combined polyether, which has the characteristics of stable and transparent system, low viscosity, good atomization and excellent flame retardant effect; the invention also provides a preparation method and application thereof.

The pentane spraying type polyurethane combined polyether comprises the following raw materials in parts by weight:

the polyether polyol A is polyether polyol which uses sucrose as one or all of the initiators, has the functionality of 4.5-7.5 and the hydroxyl value of 350-500 mgKOH/g; the preferred materials are INOVOL R5118G and INOVOL R8345 from Shandong-Noway New Material Co.

The polyether polyol C is polyether polyol which uses ethylenediamine as one or all of the initiators, the functionality is 3.5-4.5, and the hydroxyl value is 700-800 mgKOH/g; InOVOL R403, New materials, Norway, Shandong, is preferred.

The polyether polyol D is polyether polyol which uses glycerol as one or all of the initiators, has the functionality of 2.5-3.5 and the hydroxyl value of 150-500 mgKOH/g; InOVOL C310 and INOVOL C303, from Shandong-Noway New Material Co., Ltd, are preferred.

The polyester polyol B is phthalic anhydride polyester polyol, the functionality is 2-2.5, and the hydroxyl value is 150-350 mgKOH/g; preferably B175 from Shandong-Nowegian polyurethane corporation or PS2352/2412 from Stropan chemical corporation.

The catalyst is a mixture of a tertiary amine hydrolysis-resistant catalyst and an organic metal catalyst. Preferably a mixture of bis (dimethylaminoethyl) ether (A1), pentamethyldiethylenetriamine (PC5), a 33% triethylene diamine solution (A33), tris (dimethylaminopropyl) hexahydrotriazine (PC41), 2-hydroxy-N, N, N-trimethyl-1-propylamine formate (TMR-2) and potassium isooctanoate (CA50) in a mixing mass ratio of 1-4.2:1-2.5:1-3.5:1-2.5:0.3-1: 1-3.

The foam stabilizer is polyether modified organosilicon surfactant, preferably L5388 from Miigao advanced materials Co., Ltd or S1087 from Xin Shao chemical industry.

The flame retardant is a compound of an additive type halogenated phosphate flame retardant, preferably a mixture of TCPP and TEP which are contained in Zhejiang in ten thousand according to the mass ratio of 2.5-5: 1.

The chemical foaming agent is water; the pentane foaming agent is one or two of cyclopentane and isopentane.

The mass ratio of the chemical foaming agent to the pentane foaming agent is 1.7-1.9: 4.2-5.7. Under the condition of the proportion, the flame retardant property and the compression property of the foam reach the optimal balance.

The preparation method of the pentane spraying type polyurethane combined polyether comprises the following steps:

sequentially mixing polyether polyol A, polyester polyol B, polyether polyol C, polyether polyol D, silicone oil, a catalyst, a chemical foaming agent and a physical foaming agent, and stirring at normal temperature for 0.3-0.5h to obtain the pentane spraying type polyurethane combined polyether.

The application of the pentane spraying type polyurethane combined polyether is that the component A is used as a component A of pentane spraying type polyurethane foam, the component B is polymethylene polyphenyl isocyanate, and when the pentane spraying type polyurethane combined polyether is used, the component A and the component B are mixed according to the weight ratio of 100:100 and 130 for spraying, so that the pentane spraying type polyurethane foam is obtained.

According to the pentane spraying type polyurethane combined polyether, the dissolving fraction of the pentane foaming agent is improved through the matching of polyether polyol and the flame retardant, and the problem of intersolubility of the pentane foaming agent is solved; the flame retardant efficiency is improved by adjusting the compounding ratio of TCPP and TEP, and the loss of the flame retardant property of the foam caused by pentane is solved as much as possible by combining the selection of the polyol and the compounding of a catalytic system; the flame retardance reaches the standard, the system is transparent and is not layered, the spraying type combined polyether with simple construction process has the possibility of using pentane for substitution, and meanwhile, the use of n-pentane and isopentane foaming agents improves the size change rate of foam, so that the foam density of a B2 level system can be reduced to 35kg/m³Greatly reduces the material cost of spraying constructionThen, the process is carried out; while the traditional 141B type product has the advantages of ensuring the flame retardance of B2 grade and good mechanical property, the whole density needs to reach 40kg/m³。

Compared with the prior art, the invention has the following beneficial effects:

(1) the polyol compound system improves the intersolubility of pentane, and under the condition of increasing the using amount of high-flame-retardant polyester, the pentane solubility reaches 6 percent, so that the pentane foaming agent is used in a low-density spraying formula;

(2) according to the invention, the proportion of the pentane foaming agent and the chemical foaming agent is comprehensively matched, so that the highest value of the pentane addition amount to the strength improvement efficiency is obtained, the minimum value of the pentane foaming agent to the flame retardation reduction efficiency is also met, and the density of the sprayed polyurethane foam can be reduced to 35kg/m within the proportion range³The material cost of spraying construction is greatly reduced, the flame retardant requirement of B2 level can be met, and the improvement of the dimensional stability of the system by the pentane foaming agent can be exerted;

(4) the pentane spraying type polyurethane combined polyether has the characteristics of environment-friendly foaming agent and no ODS substance, the overall density and the comprehensive cost of the obtained polyurethane foam product are lower than those of the conventional 141b products, the comprehensive performance of the product meets the performance requirements of GB50404-2017, and the problem of substitution of the foaming agent in the spraying industry is solved.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention. The raw materials used in the examples and comparative examples are commercially available products.

Example 1

Polyether polyols R5118G were weighed separately: 35 parts of (B); polyester polyol PS 2352: 45 parts of (1); polyether polyol R403: 10 parts of (A); polyether polyol C310: 10 parts of (A); silicone oil L6688: 2 parts of (1); water: 3.4 parts; a1: 4 parts of a mixture; PC 5: 2 parts of (1); a33: 2.7 parts; PC 41: 1.2 parts; TMR-2: 0.4 part; CA 50: 1.2 parts; TCPP: 40 parts of a mixture; TEP: 20 parts of (1); isopentane: 9.5 parts.

And sequentially adding the weighed raw materials into a reaction kettle, stirring for 0.5 hour at normal temperature, taking out the raw materials for inspection, satisfying process parameters, sending out foam to obtain the pentane spraying type polyurethane combined polyether, taking out the pentane spraying type polyurethane combined polyether from the reaction kettle, barreling and warehousing the pentane spraying type polyurethane combined polyether serving as the component A, wherein the component A is clear and transparent.

And (3) mixing the component A and the component B (polymethylene polyphenyl isocyanate) according to the weight ratio of A to B being 100 to 110, spraying, preparing pentane spraying type polyurethane foam, and testing the quality index of the product.

Example 2

Polyether polyol R8345 was weighed separately: 40 parts of a mixture; polyester polyol PS 2412: 20 parts of polyether polyol R403: 5 parts of a mixture; polyether polyol C310: 35 parts of (B); silicone oil S1087: 2 parts of (1); water: 3.3 parts; a1: 2 parts of (1); PC 5: 2 parts of (1); a33: 3 parts of a mixture; PC 41: 2 parts of (1); TMR-2: 0.4 part; CA 50: 2.1 parts; TCPP: 60 parts; TEP: 15 parts of (1); isopentane: 8.5 parts.

And sequentially adding the weighed raw materials into a reaction kettle, stirring for 0.5 hour at normal temperature, taking out the raw materials for inspection, satisfying process parameters, sending out foam to obtain the pentane spraying type polyurethane combined polyether, taking out the pentane spraying type polyurethane combined polyether from the reaction kettle, barreling and warehousing the pentane spraying type polyurethane combined polyether serving as the component A, wherein the component A is clear and transparent.

And (3) mixing the component A and the component B (polymethylene polyphenyl isocyanate) according to the weight ratio of A to B of 100 to 130, spraying to prepare pentane spraying type polyurethane foam, and testing the quality index of the product.

Example 3

Polyether polyol R8345 was weighed separately: 5 parts of a mixture; polyester polyol B175: 85 parts of polyether polyol R403: 5 parts of a mixture; polyether polyol C310: 5 parts of a mixture; silicone oil S1087: 2 parts of (1); water: 3.6 parts; a1: 2 parts of (1); PC 5: 2 parts of (1); a33: 3 parts of a mixture; PC 41: 2 parts of (1); TMR-2: 0.9 part; CA 50: 2.1 parts; TCPP: 60 parts; TEP: 20 parts of (1); isopentane: 9 parts.

And sequentially adding the weighed raw materials into a reaction kettle, stirring for 0.5 hour at normal temperature, taking out the raw materials for inspection, satisfying process parameters, sending out foam to obtain the pentane spraying type polyurethane combined polyether, taking out the pentane spraying type polyurethane combined polyether from the reaction kettle, barreling and warehousing the pentane spraying type polyurethane combined polyether serving as the component A, wherein the component A is clear and transparent.

And (3) mixing the component A and the component B (polymethylene polyphenyl isocyanate) according to the weight ratio of A to B of 100 to 130, spraying to prepare pentane spraying type polyurethane foam, and testing the quality index of the product.

Comparative example 1

Polyether polyols R6207 were weighed separately: 50 parts of a mixture; polyester polyol PS 2352: 30 parts of (1); polyether polyol R403: 10 parts of (A); polyether polyol C310: 10 parts of (A); silicone oil L6688: 2 parts of (1); water: 3.4 parts; a1: 4 parts of a mixture; PC 5: 2 parts of (1); a33: 2.7 parts; PC 41: 1.2 parts; TMR-2: 0.4 part; CA 50: 1.2 parts; TCPP: 40 parts of a mixture; TEP: 20 parts of (1); isopentane: 9.5 parts.

And (3) sequentially adding the weighed raw materials into a reaction kettle, stirring for 0.5 hour at normal temperature, taking out the raw materials for inspection, and replacing polyether to obtain an opaque formula.

Comparative example 2

Polyether polyols R5118G were weighed separately: 35 parts of (B); polyester polyol PS 2352: 45 parts of (1); polyether polyol R403: 10 parts of (A); polyether polyol C310: 10 parts of (A); silicone oil L6688: 2 parts of (1); water: 3.9 parts; a1: 4 parts of a mixture; PC 5: 2 parts of (1); a33: 2.7 parts; PC 41: 1.2 parts; TMR-2: 0.4 part; CA 50: 1.2 parts; TCPP: 40 parts of a mixture; TEP: 20 parts of (1); isopentane: 6.8 parts.

And sequentially adding the weighed raw materials into a reaction kettle, stirring for 0.5 hour at normal temperature, taking out the raw materials for inspection, satisfying process parameters, sending out foam to obtain the pentane spraying type polyurethane combined polyether, taking out the pentane spraying type polyurethane combined polyether from the reaction kettle, barreling and warehousing the pentane spraying type polyurethane combined polyether serving as the component A, wherein the component A is clear and transparent.

And (3) mixing the component A and the component B (polymethylene polyphenyl isocyanate) according to the weight ratio of A to B being 100 to 100, spraying, preparing pentane spraying type polyurethane foam, and testing the quality index of the product.

Comparative example 3

Polyether polyols R5118G were weighed separately: 35 parts of (B); polyester polyol PS 2352: 45 parts of (1); polyether polyol R403: 10 parts of (A); polyether polyol C310: 10 parts of (A); silicone oil L6688: 2 parts of (1); water: 3 parts of a mixture; a1: 4 parts of a mixture; PC 5: 2 parts of (1); a33: 2.7 parts; PC 41: 1.2 parts; TMR-2: 0.4 part; CA 50: 1.2 parts; TCPP: 40 parts of a mixture; TEP: 20 parts of (1); isopentane: 11 parts.

And sequentially adding the weighed raw materials into a reaction kettle, stirring for 0.5 hour at normal temperature, taking out the raw materials for inspection, satisfying process parameters, sending out foam to obtain the pentane spraying type polyurethane combined polyether, taking out the pentane spraying type polyurethane combined polyether from the reaction kettle, barreling and warehousing the pentane spraying type polyurethane combined polyether serving as the component A, wherein the component A is clear and transparent.

And (3) mixing the component A and the component B (polymethylene polyphenyl isocyanate) according to the weight ratio of A to B being 100 to 100, spraying, preparing pentane spraying type polyurethane foam, and testing the quality index of the product.

Comparative example 4

Polyether polyols R5118G were weighed separately: 35 parts of (B); polyester polyol PS 2352: 45 parts of (1); polyether polyol R403: 10 parts of (A); polyether polyol C310: 10 parts of (A); silicone oil L6688: 2 parts of (1); water: 3.4 parts; a1: 4 parts of a mixture; PC 5: 2 parts of (1); a33: 2.7 parts; PC 41: 1.2 parts; TMR-2: 0.4 part; CA 50: 1.2 parts; TCPP: 40 parts of a mixture; TEP: 20 parts of (1); 141 b: 16 parts of.

And sequentially adding the weighed raw materials into a reaction kettle, stirring for 0.5 hour at normal temperature, taking out the raw materials for inspection, satisfying process parameters, sending out foam to obtain the spray-coating polyurethane combined polyether, taking out the spray-coating polyurethane combined polyether from the reaction kettle, barreling and warehousing the spray-coating polyurethane combined polyether as a component A, wherein the component A is clear and transparent.

And (3) mixing the component A and the component B (polymethylene polyphenyl isocyanate) according to the weight ratio of A to B being 100 to 100, spraying to prepare spraying type polyurethane foam, and testing the quality index of the product.

Pentane spray polyurethane foams prepared in examples 1-3 and comparative examples 1-4 were tested for energy in reference to standard GB50404-2017, where the bond strength was tested for fracture in a manner that the fracture occurred from the interior of the foam. The test results are shown in table 1.

TABLE 1 test results of the properties of pentane spray polyurethane foams prepared in examples 1-3 and comparative examples 1-4