All-water spray-type hard polyurethane combined polyether and its application

Abstract

The present application relates to a kind of full water spray type hard polyurethane with combined polyether and its application, belong to combined polyether technical field.The full water spray type hard polyurethane with combined polyether described in the application is composed of polyether polyol A / B / D / E, polyester polyol C, composite catalyst, flame retardant, surfactant, chemical foaming agent and emulsifier, the combined polyether described in the application is mixed with polyisocyanate to make full water spray type hard polyurethane foam.The full water spray type hard polyurethane with combined polyether provided in the application can meet the proportioning requirement of more than 80% of the spraying machine used in market, material viscosity is low, emulsification atomization is good, there is no problem of crispness after foam forming, and size stability is good.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of full water spray type hard polyurethane with combined polyether and its application, belong to combined polyether technical field. BACKGROUND

[0002] Polyurethane foam has excellent thermal insulation performance, spray type polyurethane product is widely used in building external wall insulation and cold storage construction, has many advantages such as strong adhesion to substrate, wind pressure resistance does not fall off.

[0003] At present, the alternative scheme of foaming agent in domestic spraying industry is not clear, the alternative scheme used more in North America is 245fa substitution and LBA substitution, the technology is relatively mature, but since the prices of the two foaming agents are all 60,000 yuan / ton, the average combined material cost is more than 20,000 yuan, the comprehensive cost is too high, which is not suitable for the domestic situation, and it is difficult to popularize. Water, as a natural chemical foaming agent, has been used in the field of polyurethane for a long time, but if water is used as the foaming agent of the system completely alone, there will be many problems such as the following: the reaction system index is low due to the consumption of isocyanate in water reaction, the foam shrinks; the material viscosity is high due to the lack of physical foaming agent, which makes it difficult to atomize and mix; the material emulsification is slow, which causes the material to flow after spraying; a large amount of water reacts with isocyanate, which causes the foam to be brittle and difficult to be constructed in winter; the internal cracking is caused by slow crosslinking and curing of foam reaction, and many other problems. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application aims to provide a combined polyether for full water spray type hard polyurethane, which can meet the proportioning requirements of more than 80% of the spraying machines on the market, has low material viscosity, good emulsification and atomization, no problem of brittleness after foam forming, and stable dimensional stability; and can replace 245fa spraying products in the market to some extent.

[0005] The combined polyether for full water spray type hard polyurethane, comprising the following raw materials in parts by mass:

[0006] 10-50 parts of polyether polyol A,

[0007] 10-40 parts of polyether polyol B,

[0008] 5-30 parts of polyester polyol C,

[0009] 5-20 parts of polyether polyol D,

[0010] 10-15 parts of polyether polyol E,

[0011] 9.7-12 parts of composite catalyst,

[0012] 45-60 parts of flame retardant,

[0013] Surfactant 2-4 parts,

[0014] Chemical foaming agent 2-3.7 parts,

[0015] Emulsifier 0.6-2.1 parts;

[0016] Wherein:

[0017] The polyether polyol A is a sorbitol polyether polyol, the functionality is 4-6, the hydroxyl value is 230-340 mgKOH / g, and the viscosity is 1000-2500 mPa·s; preferably INOVOL R6200 and INOVOL R6332 of Shandong INOVOL New Material Co., Ltd.

[0018] The polyether polyol B is a sucrose and diethylene glycol compound initiator polyether polyol, the functionality is 5-8, the hydroxyl value is 120-330 mgKOH / g, and the viscosity is 700-1650 mPa·s; preferably INOVOL R3003 and INOVOL R8268 of Shandong INOVOL New Material Co., Ltd.

[0019] The polyester polyol C is a phthalic anhydride polyester polyol, the functionality is 2-2.2, and the hydroxyl value is 200-350 mgKOH / g; preferably PS3152, PS7004, and PS7001 of Stepan.

[0020] The polyether polyol D is a hexanediamine polyether polyol, the functionality is 4, and the hydroxyl value is 700-840 mgKOH / g; preferably INOVOL R403 of Shandong INOVOL New Material Co., Ltd.

[0021] The polyether polyol E is a glycerol as a starting agent polyether polyol, the functionality is 2.5-3.5, and the hydroxyl value is 150-500 mgKOH / g; preferably INOVOL C305 and INOVOL C310 of Shandong INOVOL New Material Co., Ltd.

[0022] The composite catalyst is a mixture of a tertiary amine hydrolysis-resistant catalyst and an organic metal catalyst; preferably a mixture of PC-5, CAT-106 (Solvay, Wansheng Chemical), 33% triethylenediamine solution (A33), tris(dimethylaminopropyl)hexahydrotriazine (PC41), methyl quaternary ammonium salt (TMR-2), potassium acetate, and organic bismuth; the mass ratio is (1.5-2):(1.5-3.6):(2-3):(0.8-1.2):(0.4-0.9):(0.5-1):(0.8-2).

[0023] The flame retardant is a compound of an additive halogenated phosphate ester flame retardant; preferably a compound of TCPP and TEP of Zhejiang Wansheng, the mass ratio of which is (30-50):(10-20).

[0024] The surfactant is a non-silicon surfactant, preferably is Wanjing LK665.

[0025] The chemical foaming agent is water, preferably is deionized water.

[0026] The emulsifier is formic acid, preferably is reagent grade formic acid.

[0027] The application of the combined polyether for full-water spraying type rigid polyurethane of the application comprises the following steps:

[0028] 1) Component A: polyether polyol A, polyether polyol B, polyester polyol C, polyether polyol D, polyether polyol E, composite catalyst, chemical foaming agent, surfactant are put into a reaction kettle, stirred at room temperature for 10 min, then emulsifier and flame retardant are added, stirred at room temperature for 30 min, and component A is obtained;

[0029] 2) Component B: methyl polyphenyl isocyanate.

[0030] 3) When used, component A and component B are mixed according to a weight ratio of 100:100, and a full-water spraying type rigid polyurethane foam is obtained.

[0031] The combined polyether for full-water spraying type rigid polyurethane of the application, by selecting a polyether system, adjusting a suitable ratio and index, improving the functionality as high as possible, improving the dimensional change rate performance, ensuring the low viscosity and low hydroxyl value of the polyether, improving the crispness problem of the foam from the polyether structure, combining the use of the flame retardant to make the system have a good mixing viscosity, combining the combination and collocation of the catalyst system to solve the problems of slow emulsification initiation in the early stage and slow crosslinking in the later stage, and finally the full-water spraying product has good adhesion between the foam and the substrate, and the foam has no shrinkage and cracking after the cyclic freezing and thawing experiment from-20 DEG C to 35 DEG C.

[0032] Compared with the prior art, the application has the following beneficial effects:

[0033] 1) The combined polyether for full-water spraying type rigid polyurethane of the application can meet the use conditions of most spraying machines on the market (the mainstream spraying machine on the market is a 1:1 non-variable ratio machine), the white material and the black material of the product can meet the formula index demand according to a ratio of 1:1, and seamless switching of the materials can be realized.

[0034] 2) The combined polyether for full-water spraying type rigid polyurethane of the application has a system viscosity of 300-800 mPa·s, the use of the emulsifier makes the black and white materials have good emulsification capacity, and a spraying machine mixing pressure of 1500 psi can realize good mixing effect.

[0035] 3) The combined polyether for full-water spray type rigid polyurethane of the present application has a foaming density of 28-45 kg / m 3 , has excellent low-temperature dimensional change rate, solves the shrinkage problem that easily occurs in full-water foam at low density, and solves the burning problem that easily occurs in full-water foam at high density.

[0036] 4) The combined polyether for full-water spray type rigid polyurethane of the present application solves the common problem of brittleness of full-water foam at low temperature, can meet the process environment of 5 degrees Celsius construction, and the adhesion of the foam to the substrate can reach 100 kPa or more.

[0037] 5) The combined polyether for full-water spray type rigid polyurethane has a final foam thermal conductivity of 22-26 mW / (m·K), a substrate surface compression strength of 150 kPa or more, and a flame retardant level of CLASS-B level required by American standard ASTM-E84, meeting the requirements of rigid polyurethane foam for thermal insulation. DETAILED DESCRIPTION

[0038] The present application is further described below in conjunction with examples, but the scope of protection of the present application is not limited thereto.

[0039] All raw materials used in the examples are commercially available, except for special instructions.

[0040] Example 1

[0041] A component was prepared in a 1-ton reaction vessel by weighing: polyether polyol A (R6200 from Shandong Yinaowei New Material Co., Ltd.): 50 parts; polyether polyol B (R8268 from Shandong Yinaowei New Material Co., Ltd.): 15 parts; polyester polyol C (Stapan PS3152): 5 parts; polyether polyol D (R403 from Shandong Yinaowei New Material Co., Ltd.): 20 parts; polyether polyol E (C310 from Shandong Yinaowei New Material Co., Ltd.): 10 parts; composite catalyst: 1.5 parts of PC-5, 3.6 parts of CAT-106, 3 parts of A33, 1.2 parts of PC41, 0.9 parts of TMR-2, 0.5 parts of potassium acetate, 1 part of Kunfeng Chemical Organic Bismuth DP-02; 3.7 parts of water; 4 parts of LK665; 2.1 parts of formic acid; flame retardant TCPP: 50 parts, flame retardant TEP: 10 parts.

[0042] The weighed components, polyether polyol A, polyether polyol B, polyester polyol C, polyether polyol D, polyether polyol E, composite catalyst, chemical foaming agent, and surfactant, were sequentially added to the reaction kettle for stirring at room temperature for 10 min, and then emulsifiers and flame retardants were added for stirring at room temperature for 30 min; after detection, component A was obtained and packed in a barrel.

[0043] The B component is polymethylene polyphenyl isocyanate.

[0044] The A and B components are mixed in a weight ratio of A:B = 100:100 to prepare a full-water spray type rigid combined polyether, and the product quality indicators are tested. The A component is clear and transparent.

[0045] Example 2

[0046] The A component material was prepared in a 1-ton reaction vessel by weighing: polyether polyol A (R6332 from Shandong Yinao New Material Co., Ltd.): 10 parts; polyether polyol B (R3003 from Shandong Yinao New Material Co., Ltd.): 40 parts; polyester polyol C (Stapan PS7001): 30 parts; polyether polyol D (R403 from Shandong Yinao New Material Co., Ltd.): 5 parts; polyether polyol E (C305 from Shandong Yinao New Material Co., Ltd.): 15 parts; composite catalyst: 2 parts of PC-5, 1.5 parts of CAT106, 2 parts of A33, 0.8 parts of PC41, 0.4 parts of TMR-2, 1 part of potassium acetate, 2 parts of Kunfeng Chemical Organic Bismuth DP-02; 2 parts of water; 2 parts of LK665; 0.6 parts of formic acid; flame retardant TCPP: 35 parts, flame retardant TEP: 10 parts.

[0047] The weighed components, polyether polyol A, polyether polyol B, polyester polyol C, polyether polyol D, polyether polyol E, composite catalyst, chemical foaming agent, and surfactant, were sequentially added to the reaction kettle and stirred at room temperature for 10 min. Then, the emulsifier and flame retardant were added, and the mixture was stirred at room temperature for 30 min. After detection, the component A was obtained and filled into a barrel.

[0048] The B component is a polymeric methylene polyphenyl isocyanate.

[0049] The A and B components are mixed in a weight ratio of A:B = 100:100 to prepare a full-water spray type rigid combined polyether, and the product quality indicators are tested. The A component is clear and transparent.

[0050] Example 3

[0051] The A component material was prepared in a 1-ton reaction vessel by weighing: polyether polyol A (R6200 from Shandong Yinao New Material Co., Ltd.): 40 parts; polyether polyol B (R8268 from Shandong Yinao New Material Co., Ltd.): 10 parts; polyester polyol C (Stapan PS7001): 30 parts; polyether polyol D (R403 from Shandong Yinao New Material Co., Ltd.): 10 parts; polyether polyol E (C310 from Shandong Yinao New Material Co., Ltd.): 10 parts; composite catalyst: 1.5 parts of PC-5, 3.6 parts of CAT-106, 3 parts of A33, 1.2 parts of PC41, 0.9 parts of TMR-2, 1 part of potassium acetate, 0.8 parts of Kunfeng Chemical Organic Bismuth DP-02; 3.2 parts of water; 4 parts of LK665; 1.8 parts of formic acid; flame retardant TCPP: 30 parts, flame retardant TEP: 20 parts.

[0052] The weighed components polyether polyol A, polyether polyol B, polyester polyol C, polyether polyol D, polyether polyol E, composite catalyst, chemical foaming agent, and surfactant are sequentially put into a reaction kettle and stirred at room temperature for 10 min, and then the emulsifier and flame retardant are added and stirred at room temperature for 30 min; the component A can be obtained after passing the detection and being filled in a barrel.

[0053] The component B is a polymethylene polyphenyl isocyanate.

[0054] The A and B component materials are mixed according to the weight ratio of A:B = 100:100 to prepare a full-water spray type hard combined polyether, and the product quality indicators are tested. The component A is clear and transparent.

[0055] Comparative Example 1

[0056] The component A is prepared in a 1-ton reaction vessel, and the following components are weighed: polyether polyol A (R6048 from Shandong Yinaowei New Material Co., Ltd.): 50 parts; polyether polyol B (R4110 from Shandong Yinaowei New Material Co., Ltd.): 15 parts; polyester polyol C (PS3152 from Staben): 5 parts; polyether polyol D (R403 from Shandong Yinaowei New Material Co., Ltd.): 20 parts; polyether polyol E (C310 from Shandong Yinaowei New Material Co., Ltd.): 10 parts; composite catalyst: 1.5 parts of PC-5, 3.6 parts of CAT-106, 3 parts of A33, 1.2 parts of PC41, 0.9 parts of TMR-2, 0.5 parts of potassium acetate, 1 part of Kunfeng Chemical Organic Bismuth DP-02; 3 parts of water; 4 parts of LK665; 1.7 parts of formic acid; flame retardant TCPP: 30 parts, and flame retardant TEP: 10 parts.

[0057] The weighed components polyether polyol A, polyether polyol B, polyester polyol C, polyether polyol D, polyether polyol E, composite catalyst, chemical foaming agent, and surfactant are sequentially put into a reaction kettle and stirred at room temperature for 10 min, and then the emulsifier and flame retardant are added and stirred at room temperature for 30 min; the component A can be obtained after passing the detection and being filled in a barrel.

[0058] The component B is a polymethylene polyphenyl isocyanate.

[0059] The A and B component materials are mixed according to the weight ratio of A:B = 100:100 to prepare a full-water spray type hard combined polyether, and the product quality indicators are tested. The component A is clear and transparent.

[0060] Comparative Example 2

[0061] The A component material was prepared in a 1-ton reaction vessel. The following components were weighed: polyether polyol A (Shandong Yinao Wei New Material Co., Ltd. R6332): 0 parts; polyether polyol B (Shandong Yinao Wei New Material Co., Ltd. R3003): 55 parts; polyester polyol C (Stapan PS3152): 15 parts; polyether polyol D (Shandong Yinao Wei New Material Co., Ltd. R403): 20 parts; polyether polyol E (Shandong Yinao Wei New Material Co., Ltd. C310): 10 parts; composite catalyst: 2 parts PC-5, 1.5 parts CAT-106, 2 parts A33, 0.8 parts PC41, 0.4 parts TMR-2, 1 part potassium acetate, 2 parts Kunfeng Chemical Organic Bismuth DP-02; 2 parts water; 2 parts LK665; 0.6 parts formic acid; flame retardant TCPP: 30 parts, flame retardant TEP: 10 parts.

[0062] The weighed components, polyether polyol A, polyether polyol B, polyester polyol C, polyether polyol D, polyether polyol E, composite catalyst, chemical foaming agent, and surfactant, were sequentially added to the reaction kettle and stirred at room temperature for 10 min. Then, the emulsifier and flame retardant were added, and the mixture was stirred at room temperature for 30 min. The A component was obtained after passing the quality inspection and being packed in a barrel.

[0063] The B component was polymethylene polyphenyl isocyanate.

[0064] The A and B components were mixed in a weight ratio of A:B = 100:100 to prepare a full-water spray type hard polyether combination, and the product quality indicators were tested. The A component was clear and transparent.

[0065]

Claims

1. A combined polyether for full water spray type rigid polyurethane characterized by, The raw materials include the following mass fractions: polyether polyol A 10-50 parts, polyether polyol B 10-40 parts, polyester polyol C 5-30 parts, polyether polyol D 5-20 parts, polyether polyol E 10-15 parts, composite catalyst 9.7-12 parts, flame retardant 45-60 parts, surfactant 2-4 parts, chemical foaming agent 2-3.7 parts, emulsifier 0.6-2.1 parts; wherein: the polyether polyol A is a sorbitol polyether polyol, with a functionality of 4-6, a hydroxyl value of 230-340 mgKOH / g, and a viscosity of 1000-2500 mPa·s; the polyether polyol B is a sucrose and diethylene glycol compound initiator polyether polyol, with a functionality of 5-8, a hydroxyl value of 120-330 mgKOH / g, and a viscosity of 700-1650 mPa·s; the polyester polyol C is a phthalic anhydride polyester polyol, with a functionality of 2-2.2 and a hydroxyl value of 200-350 mgKOH / g; the polyether polyol D is a hexanediamine polyether polyol, with a functionality of 4 and a hydroxyl value of 700-840 mgKOH / g; the polyether polyol E is a glycerol initiator polyether polyol, with a functionality of 2.5-3.5 and a hydroxyl value of 150-500 mgKOH / g; the composite catalyst is a mixture of a tertiary amine hydrolysis-resistant catalyst and an organic metal catalyst; the composite catalyst is a mixture of PC-5, CAT-106, 33% triethylenediamine solution A33, tris(dimethylaminopropyl)hexahydrotriazine PC41, methyl quaternary ammonium salt TMR-2, potassium acetate, and organic bismuth, with a mass ratio of (1.5-2):(1.5-3.6):(2-3):(0.8-1.2):(0.4-0.9):(0.5-1):(0.8-2); the emulsifier is formic acid; the chemical foaming agent is water.

2. The combined polyether for all-aqueous spray-type rigid polyurethane according to claim 1, characterized by, The flame retardant is a compound of an additive halogenated phosphate ester flame retardant.

3. The combined polyether for full water spray type rigid polyurethane according to claim 2, characterized by, The flame retardant is a compound of TCPP and TEP, with a mass ratio of (30-50):(10-20).

4. The combined polyether for all-aqueous spray-type rigid polyurethane according to claim 1, characterized by, The surfactant is a non-silicon surfactant.

5. Use of the combined polyether of any one of claims 1 to 4 for all- water sprayable rigid polyurethane, characterized in that, The method includes the following steps: 1) Component A: polyether polyol A, polyether polyol B, polyester polyol C, polyether polyol D, polyether polyol E, composite catalyst, chemical foaming agent, and surfactant are put into a reaction kettle and stirred uniformly, followed by adding emulsifier and flame retardant and stirring uniformly to obtain component A; 2) Component B: methyl polyphenyl isocyanate.

6. Use of a combined polyether according to claim 5 for all- water sprayable rigid polyurethane, characterized in that, Component A and component B are mixed in proportion to obtain a full-water spray type rigid polyurethane foam.

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