Single-component bio-based polyurethane foam joint mixture and application thereof

Abstract

The invention provides a single-component bio-based polyurethane foam joint mixture and application thereof, and belongs to the technical field of polyurethane foam joint mixtures. The single-component bio-based polyurethane foam joint mixture provided by the invention is prepared from the following raw materials in percentage by mass: 10 to 30 percent of bio-based polyol, 20 to 60 percent of isocyanate, 0.3 to 1 percent of catalyst, 5 to 30 percent of plasticizer, 0.4 to 3 percent of foam stabilizer, 10 to 25 percent of foaming agent and 0 to 0.5 percent of essence. According to the invention, the bio-based polyol is adopted as a raw material, compared with a petroleum-based raw material, the toxicity is lower, the source is richer, the price is lower, the structure is more diversified, green and environment-friendly, and the prepared polyurethane foam joint mixture has excellent comprehensive performance.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane foam sealants, and in particular relates to a single-component bio-based polyurethane foam sealant and application thereof. Background Art

[0002] One-component polyurethane foam sealant (OCF for short) is a special moisture-curing rigid polyurethane foam system, which is composed of polyurethane prepolymer, catalyst, foaming agent, etc. loaded in a pressure-resistant aerosol can. When the material is sprayed from the can into holes or gaps, it quickly foams and expands and reacts with moisture in the air or on the substrate to solidify. The solidified foam has multiple effects such as filling, bonding, sealing and heat insulation, and is widely used in various fields.

[0003] At present, in the preparation process of OCF in China, the main raw materials polyols and isocyanates are petroleum-based products. Petroleum is a non-renewable resource, and the preparation of OCF with green renewable biomass resources has become an important development direction, but the application of bio-based raw materials in OCF has not been reported. Summary of the invention

[0004] The purpose of the present invention is to provide a one-component bio-based polyurethane foam sealant and its application. The raw material of the polyurethane foam sealant provided by the present invention is a bio-based material, which is green and environmentally friendly and has excellent comprehensive performance.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The invention provides a one-component bio-based polyurethane foam sealant, which is prepared from the following raw materials, calculated by mass percentage: 10-30% of bio-based polyol, 20-60% of isocyanate, 0.3-1% of catalyst, 5-30% of plasticizer, 0.4-3% of foam stabilizer, 10-25% of blowing agent and 0-0.5% of flavor.

[0007] Preferably, the bio-based polyol includes at least one of soybean oil-based polyol, castor oil-based polyol, rapeseed liquefied polyol, palm oil-based polyol, rapeseed oil-based polyol, lignin-based polyol, rosin ester polyol, polylactide polyol and multifunctional bio-based polyester polyol.

[0008] Preferably, the functionality of the bio-based polyol is 2 to 4, the number average molecular weight is 400 to 10,000, and the hydroxyl value is 100 to 450 mg KOH / g.

[0009] Preferably, the isocyanate comprises bio-based isocyanate and / or polyphenyl polymethylene polyisocyanate.

[0010] Preferably, the functionality of the bio-based isocyanate is 2.2 to 2.9.

[0011] Preferably, the catalyst is bismorpholine diethyl ether.

[0012] Preferably, the plasticizer includes at least one of a bio-based plasticizer, an environmentally friendly phosphate ester plasticizer, and a natural fatty acid ester plasticizer.

[0013] Preferably, the foam stabilizer comprises polyethylene oxide and polypropylene oxide graft-modified silane.

[0014] Preferably, the blowing agent includes at least one of dimethyl ether, propane and butane and 1,1,1,2-tetrafluoroethane.

[0015] The present invention also provides the use of the one-component bio-based polyurethane foam sealant described in the above technical solution in the fields of building sealing, waterproofing, heat insulation and bonding.

[0016] The present invention provides a one-component bio-based polyurethane foam sealant, which is prepared from the following raw materials, measured by mass percentage: 10-30% bio-based polyol, 20-60% isocyanate, 0.3-1% catalyst, 5-30% plasticizer, 0.4-3% foam stabilizer, 10-25% blowing agent and 0-0.5% flavor. The present invention uses bio-based polyol as a raw material, which is less toxic, more abundant in source, lower in price, more diverse in structure, green and environmentally friendly than petroleum-based raw materials, and the prepared polyurethane foam sealant has excellent comprehensive performance. The results of the embodiment show that the thermal conductivity of the one-component bio-based polyurethane foam sealant provided by the present invention is not more than 0.05W / (m · K), the 7d tensile bond strength under standard conditions is not less than 53kPa, the 7d tensile bond strength under water immersion conditions is not less than 45kPa, and the shear strength is not less than 63kPa. DETAILED DESCRIPTION

[0017] The invention provides a one-component bio-based polyurethane foam sealant, which is prepared from the following raw materials, calculated by mass percentage: 10-30% of bio-based polyol, 20-60% of isocyanate, 0.3-1% of catalyst, 5-30% of plasticizer, 0.4-3% of foam stabilizer, 10-25% of blowing agent and 0-0.5% of flavor.

[0018] The raw materials for preparing the one-component bio-based polyurethane foam sealant of the present invention include 10-30% of bio-based polyols by mass percentage. In an embodiment of the present invention, the amount of the bio-based polyols can be specifically 10%, 15%, 20%, 25% or 30%.

[0019] In the present invention, the bio-based polyol preferably includes at least one of soybean oil-based polyol, castor oil-based polyol, rapeseed stalk liquefied polyol, palm oil-based polyol, rapeseed oil-based polyol, lignin-based polyol, rosin ester polyol, polylactide polyol and multifunctional bio-based polyester polyol.

[0020] In the present invention, the functionality of the bio-based polyol is preferably 2 to 4; the number average molecular weight of the bio-based polyol is preferably 400 to 10,000; and the hydroxyl value of the bio-based polyol is preferably 100 to 450 mgKOH / g. The present invention limits the amount and parameters of the bio-based polyol to the above range, which can further improve the comprehensive performance of the polyurethane foam sealant.

[0021] The present invention has no particular limitation on the source of the bio-based polyol, and commercially available products known to those skilled in the art can be used. In the present invention, the palm oil-based polyol preferably includes PKF3000 and PK317 produced by Maskimi of Malaysia and PKF3000 and PKF317 produced by PCC Rokita SA of Poland. G1000 products; the soybean oil-based polyol preferably includes the SoyOyl P38.GC5 and / or SoyOyl P38-05 products produced by Urethane Soy Systems Co. (USSC) of the United States; the castor oil-based polyol is preferably Polycin GR-160 and / or Polycin GR-220 produced by Vertellus Performance Materials Co., Ltd. of the United States; the rosin ester polyol is preferably the PC300A product produced by Jiangsu Qianglin Bioenergy Co., Ltd.; the polylactide polyol is preferably the polylactide diol produced by Shenzhen Guanghua Weiye Co., Ltd.; the lignin-based polyol is preferably a product with a hydroxyl value ≥420mg KOH / g and a functionality >3 produced by Changzhou Shanfeng Chemical Co., Ltd.

[0022] The raw materials for preparing the one-component bio-based polyurethane foam sealant of the present invention include 20-60% isocyanate by mass percentage. In an embodiment of the present invention, the amount of the isocyanate can be specifically 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%. The present invention limits the amount of isocyanate to the above range, which can further improve the comprehensive performance of the polyurethane foam sealant.

[0023] In the present invention, the isocyanate preferably includes bio-based isocyanate and / or polyphenyl polymethylene polyisocyanate.

[0024] In the present invention, the bio-based isocyanate preferably includes polyisocyanate synthesized using soybean oil, castor oil, oleic acid, amino acid and / or lysine as raw materials.

[0025] In the present invention, the functionality of the bio-based isocyanate is preferably 2.2 to 2.9.

[0026] In the present invention, the polyphenyl polymethylene polyisocyanate preferably includes one or more of PAPI and TDI and modified products thereof.

[0027] The present invention has no particular limitation on the source of the isocyanate, and commercial products known to those skilled in the art can be used. In the present invention, the isocyanate preferably includes products with the grades of SUP5005 and SUP2085 produced by HUNTSMAN CORP., products with the grade of M20S produced by BASF CORP., products with the grade of 44V20L produced by BAYER CORP., or products with the grade of PM-200 produced by Yantai Wanhua Polyurethane Co., Ltd.

[0028] The raw materials for preparing the one-component bio-based polyurethane foam sealant of the present invention include 0.3-1% of catalyst by mass percentage. In the embodiment of the present invention, the amount of the catalyst can be specifically 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%. The present invention limits the amount of the catalyst to the above range, which can further improve the comprehensive performance of the polyurethane foam sealant.

[0029] In the present invention, the catalyst is preferably bismorpholine diethyl ether. The present invention has no particular limitation on the source of the catalyst, and a commercial product known to those skilled in the art can be used. In an embodiment of the present invention, the catalyst is JEFFCAT DMDEE from Huntsman, USA.

[0030] The raw materials for preparing the one-component bio-based polyurethane foam sealant of the present invention include 5-30% of plasticizer by mass percentage. In an embodiment of the present invention, the amount of the plasticizer can be specifically 5%, 10%, 15%, 20%, 25% or 30%. The present invention limits the amount of the plasticizer to the above range, which can further improve the comprehensive performance of the polyurethane foam sealant.

[0031] In the present invention, the plasticizer preferably includes at least one of a bio-based plasticizer, an environmentally friendly phosphate plasticizer and a natural fatty acid ester plasticizer, and more preferably chloromethoxy fatty acid methyl ester or a mixture of soybean oil and chloromethoxy fatty acid methyl ester.

[0032] The present invention has no particular limitation on the source of the plasticizer, and commercially available products known to those skilled in the art can be used. In the present invention, the chloromethoxy fatty acid methyl ester is preferably chloromethoxy fatty acid methyl ester produced by Hebei Xinji Chenxu Plastic Chemical Co., Ltd.

[0033] The raw materials for preparing the one-component bio-based polyurethane foam sealant of the present invention include 0.4-3% of foam stabilizer by mass percentage. In the embodiment of the present invention, the amount of the foam stabilizer can be specifically 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5% or 3%. The present invention limits the amount of the foam stabilizer to the above range, which can further improve the comprehensive performance of the polyurethane foam sealant.

[0034] In the present invention, the foam stabilizer preferably includes polyethylene oxide and polyoxypropylene grafted modified silane. The present invention has no special limitation on the source of the foam stabilizer, and commercially available products known to those skilled in the art can be used. In the present invention, the foam stabilizer preferably includes products with the grades B8871 and B84811 produced by Evonik of Germany, products with the grades L-5356, L-5440, L-5420 and L-5421 produced by Momentive of the United States, or products with the grades DC5604, DC193 and DC5589 produced by Gas Products of the United States.

[0035] The raw materials for preparing the one-component bio-based polyurethane foam sealant of the present invention include 10-25% of a foaming agent by mass percentage. In an embodiment of the present invention, the amount of the foaming agent can be specifically 10%, 15%, 20% or 25%. The present invention limits the amount of the foaming agent to the above range, which can further improve the comprehensive performance of the polyurethane foam sealant.

[0036] In the present invention, the foaming agent preferably includes at least one of dimethyl ether, propane and 1,1,1,2-tetrafluoroethane.

[0037] The present invention has no particular limitation on the source of the foaming agent, and commercially available products known to those skilled in the art may be used.

[0038] The raw materials for preparing the one-component bio-based polyurethane foam sealant of the present invention include 0-0.5% of flavor in terms of mass percentage. In an embodiment of the present invention, the amount of the flavor can be specifically 0%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%.

[0039] The present invention has no special limitation on the type and source of the flavor, and can be selected according to actual needs. In the present invention, the flavor preferably includes at least one of lemon flavor, orange flavor, lavender flavor and osmanthus flavor.

[0040] The present invention adopts bio-based polyol as raw material, and can also adopt bio-based isocyanate, so that the polyurethane foam sealant is closer to complete bio-based, which is beneficial to the degradation of the product. Compared with petroleum-based raw materials, it has lower toxicity, more abundant sources, lower prices, more diverse structures, green and environmentally friendly. The type and amount of each raw material are controlled, and the prepared polyurethane foam sealant has excellent comprehensive performance.

[0041] In the present invention, the preparation method of the one-component bio-based polyurethane foam sealant preferably comprises the following steps:

[0042] (1) mixing a catalyst, a plasticizer, a foam stabilizer and a bio-based polyol to obtain a polyurethane composition liquid;

[0043] (2) isocyanate, the polyurethane composition liquid obtained in step (1) and a foaming agent are sequentially charged into an aerosol can to obtain a one-component bio-based polyurethane foam sealant.

[0044] The present invention preferably mixes a catalyst, a plasticizer, a foam stabilizer and a bio-based polyol to obtain a polyurethane composition liquid.

[0045] In the present invention, when the one-component bio-based polyurethane foam sealant contains fragrance, the present invention preferably mixes the catalyst, the plasticizer, the foam stabilizer, the bio-based polyol and the fragrance to obtain the polyurethane composition liquid.

[0046] In the present invention, the mixing is preferably carried out under stirring conditions; the stirring rate is preferably 1000 to 2000 rpm; and the stirring time is preferably 20 to 40 min.

[0047] After obtaining the polyurethane composition liquid, the present invention preferably sequentially fills the isocyanate, the polyurethane composition liquid and the foaming agent into an aerosol can to obtain a single-component bio-based polyurethane foam sealant.

[0048] The present invention has no special limitation on the operation of sequentially charging the isocyanate, the polyurethane composition liquid and the foaming agent into the aerosol can, and the technical scheme well known to those skilled in the art can be adopted.

[0049] The present invention also provides the use of the one-component bio-based polyurethane foam sealant described in the above technical solution in the fields of building sealing, waterproofing, heat insulation and bonding.

[0050] The present invention has no special limitation on the operation of the application, and the technical solutions of the application well known to those skilled in the art may be adopted.

[0051] The single-component bio-based polyurethane foam sealant provided by the present invention adopts bio-based raw materials, which is more conducive to the degradation and renewability of the polyurethane foam sealant.

[0052] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0053] Example 1

[0054] The one-component bio-based polyurethane foam sealant is prepared from the following raw materials, calculated by mass percentage: 10% bio-based polyol (7% palm oil-based polyol, produced by Maskimi, Malaysia, with the brand name PKF3000; 3% soybean oil-based polyol, produced by Urethane Soy Systems, USA) Co. (USSC company) with the brand name SoyOylP38.GC5), polyphenyl polymethylene polyisocyanate 60% (functionality 2.6-2.7, Wanhua PM-200), bismorpholine diethyl ether catalyst 1% (JEFFCATDMDEE of Huntsman Company, USA), chloromethoxy fatty acid methyl ester plasticizer 6.7% (Hebei Xinji Chenxu Plastic Chemical Co., Ltd.), foam stabilizer 2% (B8871 of Evonik Company, Germany), foaming agent 20% (a mixture of dimethyl ether, propane and 1,1,1,2-tetrafluoroethane in a mass ratio of 5:5:10) and lemon essence 0.3% (Shanghai Tianyi Flavor and Fragrance Co., Ltd., brand name: TY88852);

[0055] The preparation method of the one-component bio-based polyurethane foam sealant is as follows: (1) mixing a catalyst, a plasticizer, a foam stabilizer, a bio-based polyol and a lemon essence, and stirring at 1500 rpm for 30 minutes to obtain a polyurethane composite liquid;

[0056] (2) isocyanate, the polyurethane composition liquid obtained in step (1) and a foaming agent are sequentially charged into an aerosol can to obtain a one-component bio-based polyurethane foam sealant.

[0057] Example 2

[0058] A one-component bio-based polyurethane foam sealant is prepared from the following raw materials, calculated by mass percentage: 16% bio-based polyol (12% palm oil-based polyol, 4% castor oil-based polyol), 54.7% polyphenyl polymethylene polyisocyanate (functionality of 2.6-2.7, Wanhua PM-200), 0.8% bismorpholine diethyl ether catalyst (JEFFCAT DMDEE from Huntsman, USA), 8.3% chloromethoxy fatty acid methyl ester plasticizer (Hebei Xinji Chenxu Plastic Chemical Co., Ltd.), 2.2% foam stabilizer (L-5356 from Momentive, USA) and 18% foaming agent (a mixture of dimethyl ether, propane and 1,1,1,2-tetrafluoroethane in a mass ratio of 6:6:8); wherein the castor oil-based polyol is Polycin GR-160 from Vertellus Specialty Materials Co., Ltd. of the United States; and the palm oil-based polyol is PK317 produced by Maskimi, Malaysia.

[0059] The preparation method of the one-component bio-based polyurethane foam sealant is the same as that in Example 1.

[0060] Example 3

[0061] The one-component bio-based polyurethane foam sealant is prepared from the following raw materials, calculated by mass percentage: 20% bio-based polyol (10% polylactide polyol, 10% soybean oil-based polyol), 49.4% polyphenyl polymethylene polyisocyanate (functionality 2.6-2.7, Wanhua PM-200), 0.9% bismorpholine diethyl ether catalyst (JEFFCAT, Huntsman, USA) DMDEE), chloromethoxy fatty acid methyl ester plasticizer 7.6% (Hebei Xinji Chenxu Plastic Chemical Co., Ltd.), foam stabilizer 2.1% (a mixture of L-5356 from Momentive Corporation of the United States and B84811 from Evonik of Germany, the mass ratio of L-5356 to B84811 being 2:1) and foaming agent 20% (a mixture of dimethyl ether, propane and 1,1,1,2-tetrafluoroethane in a mass ratio of 6:6:8); wherein the polylactide polyol is the polylactide diol of Shenzhen Guanghua Weiye Co., Ltd.; the soybean oil-based polyol is the brand SoyOylP38.GC5 produced by Urethane Soy Systems Co. (USSC) of the United States;

[0062] The preparation method of the one-component bio-based polyurethane foam sealant is the same as that in Example 1.

[0063] Example 4

[0064] The one-component bio-based polyurethane foam sealant is prepared from the following raw materials, calculated by mass percentage: 27% bio-based polyol (15% soybean oil-based polyol, 12% rosin ester polyol), 45% bio-based isocyanate (functionality 2.2-2.9, Japan Mitsui Chemicals, bio-based isocyanate D-3725N), 0.9% bismorpholine diethyl ether catalyst (JEFFCAT DMDEE of Huntsman Company, USA), 7.6% chloromethoxy fatty acid methyl ester plasticizer (Hebei Xinji Chenxu Plastic Chemical Co., Ltd.), 2.5% foam stabilizer (L-5356 of Momentive Company, USA) and 17% foaming agent (a mixture of dimethyl ether, propane and 1,1,1,2-tetrafluoroethane in a mass ratio of 6:6:8); wherein the soybean oil-based polyol is produced by UrethaneSoy Systems Co. (USSC Company) of the United States and is branded as SoyOyl P38.GC5; rosin ester polyol is PC300A produced by Jiangsu Qianglin Bioenergy Co., Ltd.;

[0065] The preparation method of the one-component bio-based polyurethane foam sealant is the same as that in Example 1.

[0066] Example 5

[0067] The one-component bio-based polyurethane foam sealant is prepared from the following raw materials, calculated by mass percentage: 15% bio-based polyol (lignin-based polyol), 53% isocyanate (a mixture of TDI (functionality 2, BASF CORP. TDI80) and polyphenyl polymethylene polyisocyanate (functionality 2.6-2.7, Wanhua PM-200), the mass ratio of TDI to PM-200 is 1:6), 0.8% bismorpholine diethyl ether catalyst (JEFFCAT, Huntsman, USA) DMDEE), 12.2% plasticizer (a mixture of soybean oil and chloromethoxy fatty acid methyl ester plasticizer (Hebei Xinji Chenxu Plastic Chemical Co., Ltd.) in a mass ratio of 1:2), 2% foam stabilizer (B8871 from Evonik, Germany) and 17% foaming agent (a mixture of dimethyl ether and propane and butane in a mass ratio of 5:7); wherein the lignin-based polyol is a product produced by Changzhou Shanfeng Chemical Co., Ltd. with a hydroxyl value of 420 mg KOH / g and a functionality of 3;

[0068] The preparation method of the one-component bio-based polyurethane foam sealant is the same as that in Example 1.

[0069] The one-component bio-based polyurethane foam sealants in Examples 1 to 5 were made into foam samples, and their properties were tested according to the industry standard JC936-2004. The results are shown in Table 1.

[0070] Table 1 Properties of foam samples made from one-component bio-based polyurethane foam sealants in Examples 1 to 5

[0071]

[0072] It can be seen from Table 1 that the various properties of the one-component bio-based polyurethane foam sealant provided by the present invention can meet the results required by industry standards and meet the application requirements of the product.

[0073] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A one-component bio-based polyurethane foam sealant is prepared from the following raw materials, calculated by mass percentage: 10-30% of bio-based polyol, 20-60% of isocyanate, 0.3-1% of catalyst, 5-30% of plasticizer, 0.4-3% of foam stabilizer, 10-25% of blowing agent and 0-0.5% of flavor.

2. The one-component bio-based polyurethane foam sealant according to claim 1, characterized in that: The bio-based polyol includes at least one of soybean oil-based polyol, castor oil-based polyol, rapeseed liquefied polyol, palm oil-based polyol, rapeseed oil-based polyol, lignin-based polyol, rosin ester polyol, polylactide polyol and multifunctional bio-based polyester polyol.

3. The one-component bio-based polyurethane foam sealant according to claim 1 or 2, characterized in that: The functionality of the bio-based polyol is 2 to 4, the number average molecular weight is 400 to 10,000, and the hydroxyl value is 100 to 450 mg KOH / g.

4. The one-component bio-based polyurethane foam sealant according to claim 1, characterized in that: The isocyanate includes bio-based isocyanate and / or polyphenyl polymethylene polyisocyanate.

5. The one-component bio-based polyurethane foam sealant according to claim 4, characterized in that: The functionality of the bio-based isocyanate is 2.2 to 2.

9.

6. The one-component bio-based polyurethane foam sealant according to claim 1, characterized in that: The catalyst is bismorpholine diethyl ether.

7. The one-component bio-based polyurethane foam sealant according to claim 1, characterized in that: The plasticizer includes at least one of a bio-based plasticizer, an environmentally friendly phosphate plasticizer, and a natural fatty acid ester plasticizer.

8. The one-component bio-based polyurethane foam sealant according to claim 1, characterized in that: The foam stabilizer includes polyethylene oxide and polypropylene oxide grafted modified silane.

9. The one-component bio-based polyurethane foam sealant according to claim 1, characterized in that: The foaming agent includes at least one of dimethyl ether, propane and 1,1,1,2-tetrafluoroethane.

10. Use of the one-component bio-based polyurethane foam sealant according to any one of claims 1 to 9 in the fields of building sealing, waterproofing, heat insulation and bonding.

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