阅读说明：本技术 一种高储存稳定性聚氨酯组合料及其制备方法 (High-storage-stability polyurethane composite material and preparation method thereof ) 是由 赵超斌 杨庆云 于 2021-07-13 设计创作，主要内容包括：本发明公开了一种高储存稳定性聚氨酯组合料,其包括黑料和白料,所述黑料为多亚甲基多苯基异氰酸脂,所述白料包括如下重量份的组分：聚醚多元醇70～100份、聚酯多元醇10～40份、二异氰酸酯0.1～5份、阻燃剂0～10份、催化剂0.5～1.5份、发泡剂20～30份和泡沫稳定剂0.5～1份。本发明通过在含有聚醚多元醇和聚酯多元醇的白料组分中添加一定量的二异氰酸酯,利用二异氰酸酯与部分的聚醚多元醇和聚酯多元醇反应生成羟基封端的聚合物,有效改善了多元醇组分之间的相容性,提高了白料的储存稳定性,还提高了聚氨酯组合料所得泡沫塑料的力学性能。(The invention discloses a high-storage-stability polyurethane composite material, which comprises a black material and a white material, wherein the black material is polymethylene polyphenyl isocyanate, and the white material comprises the following components in parts by weight: 70-100 parts of polyether polyol, 10-40 parts of polyester polyol, 0.1-5 parts of diisocyanate, 0-10 parts of flame retardant, 0.5-1.5 parts of catalyst, 20-30 parts of foaming agent and 0.5-1 part of foam stabilizer. According to the invention, a certain amount of diisocyanate is added into the white material component containing polyether polyol and polyester polyol, and the diisocyanate reacts with part of polyether polyol and polyester polyol to generate hydroxyl-terminated polymer, so that the compatibility between the polyol components is effectively improved, the storage stability of the white material is improved, and the mechanical property of the foamed plastic obtained from the polyurethane composite material is also improved.)

1. The polyurethane composite material with high storage stability is characterized by comprising a black material and a white material, wherein the black material is polymethylene polyphenyl isocyanate, and the white material comprises the following components in parts by weight: 70-100 parts of polyether polyol, 10-40 parts of polyester polyol, 0.1-5 parts of diisocyanate, 0-10 parts of flame retardant, 0.5-1.5 parts of catalyst, 20-30 parts of foaming agent and 0.5-1 part of foam stabilizer.

2. The highly storage stable polyurethane composition of claim 1, wherein said diisocyanate comprises an aromatic diisocyanate and an aliphatic diisocyanate.

3. The polyurethane composition with high storage stability of claim 2, wherein the mass ratio of the aromatic diisocyanate to the aliphatic diisocyanate in the diisocyanate is 4:1 to 8: 1.

4. The polyurethane composition of claim 2, wherein the aromatic diisocyanate comprises at least one of 2, 4-toluene diisocyanate and diphenylmethane diisocyanate.

5. The highly storage stable polyurethane composition according to claim 2, wherein the aliphatic diisocyanate is dimer acid diisocyanate.

6. The polyurethane composition with high storage stability as claimed in claim 1, wherein the mass ratio of the black material to the white material in the polyurethane composition is 0.5: 1-1: 1.

7. The polyurethane composition with high storage stability of claim 1, wherein the flame retardant is a halogenated phosphate flame retardant, the catalyst is an amine catalyst, and the foaming agent is deionized water.

8. The polyurethane composition of claim 1, wherein the foam stabilizer is a mixture of an alkyl polyglycoside and hydroxyethyl cellulose.

9. The polyurethane composition with high storage stability of claim 1, wherein the mass ratio of the alkyl polyglycoside to the hydroxyethyl cellulose in the foam stabilizer is 1: 0.1-1: 0.5.

10. A method for using the polyurethane composition with high storage stability as set forth in any one of claims 1 to 9, comprising: uniformly mixing the black material and the white material of the polyurethane composite material, and foaming to prepare the polyurethane foamed plastic, wherein the mixing conditions are as follows: stirring at 3000-5000 RPM for 15-30 s at normal temperature.

Technical Field

The invention belongs to the technical field of polyurethane, and particularly relates to a high-storage-stability polyurethane composite material and a preparation method thereof.

Background

The polyurethane composite material is mainly used as a heat-insulating and/or waterproof material for inner and outer walls of buildings, roofs, cold storages, grain depots, chemical equipment, large storage tanks, ship bodies, air-conditioning buses and other places. The product consists of black and white materials. The white material part is generally formed by combining multiple auxiliary agents such as polyol, a catalyst, a foaming agent, a flame retardant and the like; the black material portion is typically polymethylene polyphenyl isocyanate. When in use, the foam is sprayed by high-pressure airless spraying equipment and formed by foaming on site, and has the characteristics of uniform foam holes, high strength, good low-temperature dimensional stability, low heat conductivity coefficient, strong self-adhesion, wide use temperature range, good fireproof performance, low hygroscopicity, excellent heat-insulating and waterproof performance, no toxicity, no irritation, no biological parasitism and the like.

The polyether polyol is a polyol raw material with the largest use amount in polyurethane foam plastics industry, and has the advantages of much lower price than polyester polyol, good foam performance and excellent hydrolysis resistance. And predominate in polyurethane foam polyols. However, polyester polyols have advantages over polyether polyols in terms of high foam strength, good adhesion, high elongation, and good oil resistance. Therefore, in order to combine the advantages of both and reduce the production cost of polyurethane, polyether polyol and polyester polyol are generally used as synthetic monomers of polyurethane in the prior art. Therefore, the compatibility among the components is poor, the white material component which is uniformly mixed cannot be formed, the layering is easy to occur, the storage stability is poor, and the foaming effect of the polyurethane composite material is influenced.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide a polyurethane composite material with high storage stability and a preparation method thereof.

In order to realize the purpose, the technical scheme adopted by the invention is as follows:

a high-storage-stability polyurethane composite material comprises a black material and a white material, wherein the black material is polymethylene polyphenyl isocyanate, and the white material comprises the following components in parts by weight: 70-100 parts of polyether polyol, 10-40 parts of polyester polyol, 0.1-5 parts of diisocyanate, 0-10 parts of flame retardant, 0.5-1.5 parts of catalyst, 20-30 parts of foaming agent and 0.5-1 part of foam stabilizer.

According to the invention, a certain amount of diisocyanate is added into the white material component containing polyether polyol and polyester polyol, and the diisocyanate reacts with part of polyether polyol and polyester polyol to generate hydroxyl-terminated polymer, so that the compatibility between the polyol components is effectively improved, the storage stability of the white material is improved, and the mechanical property of the foamed plastic obtained from the polyurethane composite material is also improved.

Preferably, the diisocyanate includes an aromatic diisocyanate and an aliphatic diisocyanate. When the two types of diisocyanate are added simultaneously, the compatibility between the polyol components can be improved more effectively, and the white material components are mixed uniformly.

Preferably, in the diisocyanate, the mass ratio of the aromatic diisocyanate to the aliphatic diisocyanate is 4: 1-8: 1. When the two types of diisocyanate are used in combination according to the proportion, the white material has better storage stability.

Preferably, in the diisocyanate, the mass ratio of the aromatic diisocyanate to the aliphatic diisocyanate is 6: 1. When these two types of diisocyanates are used in combination in the above proportions, the white materials have the best storage stability.

Preferably, the aromatic diisocyanate includes at least one of 2, 4-Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).

Preferably, the aliphatic diisocyanate is dimer acid diisocyanate (DDI). DDI is an environment-friendly acid diisocyanate, has the characteristics of low toxicity, no yellowing, solubility in most organic solvents, low water sensitivity, low viscosity and the like, and can be used for preparing polymers with compounds with 2 or more active hydrogen.

Preferably, the polyether polyol comprises at least one of polyoxypropylene diol, polytetrahydrofuran diol, and tetrahydrofuran-oxypropylene copolyol.

Preferably, the polyester polyol is an aromatic polyester polyol.

Preferably, in the polyurethane combined material, the mass ratio of the black material to the white material is 0.5: 1-1: 1.

Preferably, in the polyurethane composite material, the mass ratio of the black material to the white material is 0.8: 1.

Preferably, the flame retardant is a halophosphate based flame retardant, e.g., TCPP, TCEP, TDCP, and the like.

Preferably, the catalyst is an amine catalyst, such as triethanolamine, N-dimethylethanolamine, and the like.

Preferably, the foaming agent is deionized water.

Preferably, the foam stabilizer is a mixture of alkyl polyglycoside and hydroxyethyl cellulose. Researches show that when the alkyl polyglycoside and the hydroxyethyl cellulose are used in combination and added into the formula, the early viscosity of a foam mixture can be obviously improved when the polyurethane composite material is foamed, the generation of fine bubbles is facilitated, the opening ratio of a foamed product is improved, the cracking of bubbles can be prevented, and the foaming stability is improved. Meanwhile, the alkyl polyglycoside and the hydroxyethyl cellulose have certain emulsification effect, and the intersolubility of foam components can be enhanced.

Preferably, in the foam stabilizer, the mass ratio of alkyl polyglycoside to hydroxyethyl cellulose is 1: 0.1-1: 0.5. When the polyurethane composite material is used in combination according to the proportion, the foaming stability of the polyurethane composite material is better, and the aperture ratio of a foamed product is higher.

Preferably, in the foam stabilizer, the mass ratio of alkyl polyglycoside to hydroxyethyl cellulose is 1: 0.3. When the foaming agent is used in combination according to the proportion, the aperture ratio of the foaming product is highest.

The invention also provides a using method of the polyurethane composite material, which comprises the following steps: and uniformly mixing the black material and the white material of the polyurethane composite material, and foaming to prepare the polyurethane foamed plastic. Preferably, the mixing conditions are: stirring at 3000-5000 RPM for 15-30 s at normal temperature (25 ℃).

Compared with the prior art, the invention has the beneficial effects that: according to the invention, a specific amount of diisocyanate is added into the synthetic monomer polyol component of polyurethane, and the component composition and the component proportion of the diisocyanate are optimized, so that the compatibility between the polyol components is effectively improved, the storage stability of white materials is improved, and the mechanical property of the foamed plastic obtained from the polyurethane combined material is also improved. The invention also optimizes the component composition and the component proportion of the foam stabilizer of the polyurethane combined material system, effectively improves the foaming stability of the polyurethane combined material and improves the aperture ratio of the foamed plastic.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. The methods employed in the examples of the present invention are conventional in the art and the equipment used is commercially available unless otherwise specified, and "parts" are referred to as "parts by weight".

The purchase source and/or kind of the partial raw materials are defined as follows:

(1) aromatic diisocyanate, TDI, designation: TDI-65, manufacturer: basf;

(2) dimer acid diisocyanate, DDI, trade mark: DDI 40, manufacturer: new materials, inc. of henna;

(3) polyether polyols, polyoxypropylene glycols;

(4) polyester polyol, aromatic polyester polyol, brand: stepanpol, PD-70LV, manufacturer: stepan corporation;

(5) flame retardants, TCPP;

(6) catalyst, triethanolamine;

(7) polymethylene polyphenyl isocyanates, basf M20S;

(8) alkyl polyglycoside, trade name: 0810, manufacturer: wikipedia chemical Co.

Example 1

The polyurethane composite material with high storage stability comprises a black material and a white material, wherein the mass ratio of the black material to the white material is 0.5:1, the black material is polymethylene polyphenyl isocyanate, and the white material is composed of the following components in parts by weight: 70 parts of polypropylene oxide glycol, 40 parts of PD-70LV polyester polyol, 0.5 part of diisocyanate, 5 parts of TCPP, 0.5 part of triethanolamine, 20 parts of deionized water and 0.5 part of foam stabilizer; wherein the diisocyanate consists of TDI and DDI, and the mass ratio of the TDI to the DDI is 6: 1; the foam stabilizer is a mixture of alkyl polyglycoside and hydroxyethyl cellulose, and the mass ratio of the alkyl polyglycoside to the hydroxyethyl cellulose is 1: 0.3.

The preparation method of the white material comprises the following steps: putting polyoxypropylene glycol and PD-70LV polyester polyol into a reaction kettle, stirring at 3000RPM for 10s, then adding diisocyanate, stirring at 3000RPM for 20s, then adding TCPP, triethanolamine, deionized water and a foam stabilizer, and stirring at 3000RPM for 1h to obtain a white material.

The use method of the polyurethane composite material comprises the following steps: and (3) stirring the black material and the white material of the polyurethane composite material at the normal temperature (25 ℃) for 15-30 s at 3000-5000 RPM (revolutions Per minute), uniformly mixing the materials, and foaming to obtain the polyurethane foamed plastic.

Example 2

The polyurethane composite material with high storage stability comprises a black material and a white material, wherein the mass ratio of the black material to the white material is 0.8:1, the black material is polymethylene polyphenyl isocyanate, and the white material is composed of the following components in parts by weight: 85 parts of polypropylene oxide glycol, 25 parts of PD-70LV polyester polyol, 1 part of diisocyanate, 8 parts of TCPP, 1 part of triethanolamine, 25 parts of deionized water and 0.8 part of foam stabilizer; wherein the diisocyanate consists of TDI and DDI, and the mass ratio of the TDI to the DDI is 6: 1; the foam stabilizer is a mixture of alkyl polyglycoside and hydroxyethyl cellulose, and the mass ratio of the alkyl polyglycoside to the hydroxyethyl cellulose is 1: 0.3.

The preparation method of the white material is the same as that of the example 1; the method of using the polyurethane composition was the same as in example 1.

Example 3

The polyurethane composite material with high storage stability comprises a black material and a white material, wherein the mass ratio of the black material to the white material is 1:1, the black material is polymethylene polyphenyl isocyanate, and the white material is composed of the following components in parts by weight: 100 parts of polypropylene oxide glycol, 10 parts of PD-70LV polyester polyol, 1.5 parts of diisocyanate, 10 parts of TCPP, 1.5 parts of triethanolamine, 30 parts of deionized water and 1 part of foam stabilizer; wherein the diisocyanate consists of TDI and DDI, and the mass ratio of the TDI to the DDI is 6: 1; the foam stabilizer is a mixture of alkyl polyglycoside and hydroxyethyl cellulose, and the mass ratio of the alkyl polyglycoside to the hydroxyethyl cellulose is 1: 0.3.

The preparation method of the white material is the same as that of the example 1; the method of using the polyurethane composition was the same as in example 1.

Comparative example 1

The polyurethane composite material with high storage stability comprises a black material and a white material, wherein the mass ratio of the black material to the white material is 0.8:1, the black material is polymethylene polyphenyl isocyanate, and the white material is composed of the following components in parts by weight: 85 parts of polypropylene oxide glycol, 25 parts of PD-70LV polyester polyol, 8 parts of TCPP, 1 part of triethanolamine, 25 parts of deionized water and 0.8 part of foam stabilizer; wherein the foam stabilizer is a mixture of alkyl polyglycoside and hydroxyethyl cellulose, and the mass ratio of the alkyl polyglycoside to the hydroxyethyl cellulose is 1: 0.3.

Comparative example 2

The polyurethane composite material with high storage stability comprises a black material and a white material, wherein the mass ratio of the black material to the white material is 0.8:1, the black material is polymethylene polyphenyl isocyanate, and the white material is composed of the following components in parts by weight: 85 parts of polypropylene oxide glycol, 25 parts of PD-70LV polyester polyol, 1 part of diisocyanate, 8 parts of TCPP, 1 part of triethanolamine, 25 parts of deionized water and 0.8 part of foam stabilizer; wherein the diisocyanate consists of TDI and DDI, and the mass ratio of the TDI to the DDI is 6: 1; the foam stabilizer is L5540 foam stabilizer from Migao New Material (China) Co.

The preparation method of the white material is the same as that of the example 1; the method of using the polyurethane composition was the same as in example 1.

First, the performance of the white materials of examples 1 to 3 and comparative examples 1 to 2 and the obtained polyurethane foamed plastics was tested, and the results are shown in table 1.

The test items were as follows:

1. the storage stability of the white material is that whether the white material is layered or not is the normal temperature and the normal pressure;

2. the compression strength of the foamed plastic is tested according to GB/T8813-88;

3. rebound resilience of foamed plastic: testing according to GB/T6670-;

4. the open pore ratio of the foamed plastic is tested according to GB/T10799-2008.

TABLE 1

Item	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Storage stability	36 months old	44 months	38 months old	3 months old	28 months old
Compressive strength/kPa	11.2	13.5	12.0	9.3	7.6
						Rebound resilience/%)	85	90	87	80	65
Open cell content%	40.3	48.9	44.1	35.9	24.7

As can be seen from the data in Table 1, compared with comparative example 1, the white materials of examples 1 to 3 have more excellent storage stability, and no delamination occurs after being placed for more than 36 months at normal temperature and normal pressure; it is demonstrated that the addition of TDI and DDI in the formulations of the present application is effective in improving the storage stability of the white material. Compared with the comparative example 2, the polyurethane foamed plastics in the examples 1 to 3 have higher aperture ratio and mechanical property, which shows that the aperture ratio of the foamed product can be better improved and the foaming stability of the polyurethane composite material is better because the formula of the polyurethane foamed plastic adopts alkyl polyglycoside and hydroxyethyl cellulose as foam stabilizers.

Secondly, in order to investigate the influence of the component composition and the component proportion of the diisocyanate on the storage stability of the white material, test groups 1 to 7 of table 2 were designed. The diisocyanate of test groups 1-7 was used to prepare polyurethane composite materials according to the formulation of example 2 (the addition amount of the diisocyanate was 1 part), and the storage stability of the white material and the performance of the polyurethane foamed plastic were tested, and the test results are shown in table 3.

TABLE 2

Group of	Component composition and component mass ratio of diisocyanate
		Test group 1	TDI
Test group 2	DDI
		Test group 3	TDI+DDI，TDI:DDI＝3:1
Test group 4	TDI+DDI，TDI:DDI＝4:1
		Test group 5	TDI+DDI，TDI:DDI＝6:1
Test group 6	TDI+DDI，TDI:DDI＝8:1
		Test group 7	TDI+DDI，TDI:DDI＝9:1

TABLE 3

As can be seen from the data in Table 3, the simultaneous addition of TDI and DDI in the formulations of the present application is more effective in improving the storage stability of the white material than the addition of TDI (aromatic diisocyanate) or DDI (aliphatic diisocyanate) alone. Moreover, the mass ratio of TDI to DDI also has an influence on the stability of white materials; when the mass ratio of TDI to DDI is 4: 1-8: 1, the storage stability of the white material is better; the storage stability of the white material is optimal when the mass ratio of TDI to DDI is 6: 1.

Thirdly, in order to investigate the influence of the component composition and the component proportion of the foam stabilizer on the performance of the polyurethane composite material, test groups 8-14 in Table 4 are designed. Polyurethane composite materials (the addition amount of the foam stabilizer is 0.8 part) were prepared according to the formulation of example 2 by using the foam stabilizers of test groups 8 to 14, respectively, and the performance of the polyurethane foamed plastic was tested, and the test results are shown in table 5.

TABLE 4

TABLE 5

As can be seen from the data in Table 5, compared with the case that alkyl polyglycoside or hydroxyethyl cellulose is added independently, the simultaneous addition of alkyl polyglycoside and hydroxyethyl cellulose in the formula of the polyurethane composite material can improve the foaming stability of the polyurethane composite material better, so that the foamed plastic can obtain higher open cell content. Moreover, the mass ratio of alkyl polyglycoside to hydroxyethyl cellulose also has an influence on the foaming effect of the polyurethane composite material; when the mass ratio of alkyl polyglycoside to hydroxyethyl cellulose is 1: 0.1-1: 0.5, the foaming stability of the polyurethane composite material is better, and the aperture ratio of a foamed product is higher; when the mass ratio of alkyl polyglycoside to hydroxyethyl cellulose is 1:0.3, the open cell content of the polyfoam product is highest.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.