阅读说明：本技术 新型阻燃低收缩聚氨酯泡沫填缝剂 (Novel flame-retardant low-shrinkage polyurethane foam joint mixture ) 是由 王伟 丁文昌 冯树良 杨开 于 2020-06-22 设计创作，主要内容包括：本发明公开了新型阻燃低收缩聚氨酯泡沫填缝剂,包括：聚酯多元醇、聚醚多元醇、催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯,所述的阻燃剂包括反应型阻燃剂和添加型阻燃剂,本发明克服了现有技术的不足,本发明使用碱性的有机蒙脱土对填缝剂进行改性有效的对含氯阻燃剂产生的毒性物质进行中和和吸收,降低了填缝剂使用时产生的泡沫的收缩率。(The invention discloses a novel flame-retardant low-shrinkage polyurethane foam gap filler, which comprises the following components in part by weight: the halogen-free flame retardant joint filling agent comprises polyester polyol, polyether polyol, a catalyst, a flame retardant, a foam stabilizer, a foaming agent and isocyanate, wherein the flame retardant comprises a reactive flame retardant and an additive flame retardant.)

1. Novel flame-retardant low-shrinkage polyurethane foam gap filler is characterized by comprising the following components in percentage by weight: the flame retardant comprises polyester polyol, polyether polyol, a catalyst, a flame retardant, a foam stabilizer, a foaming agent and isocyanate, wherein the flame retardant comprises a reactive flame retardant and an additive flame retardant.

2. The new flame retardant low shrink polyurethane foam underfill of claim 1 wherein the reactive flame retardant is one or more of trichloroisopropyl phosphate, chlorinated paraffin, tris (dipropylene glycol) phosphite, tris (polyoxyalkylene) phosphate, tris (polyoxyalkylene) phosphite, polyether polyol solution of tris (cyanated polyol) phosphate dibromopentanediol, brominated pentaerythritol and tetrabromophthalic anhydride series flame retardant polyol, polyether Ixol B251 or polyether Ixol M125.

3. The new flame retardant low shrinkage polyurethane foam caulking agent of claim 1, wherein the additive type flame retardant is one of organo montmorillonite, tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methylphosphonate or polybromodiphenyl ether.

4. The novel flame retardant low shrink polyurethane foam caulk of claim 3 wherein said organo montmorillonite has a pH of 8-9.

5. The novel flame-retardant low-shrinkage polyurethane foam gap filler as claimed in claim 1, wherein the functionality of the polyester polyol is 2-4, the molecular weight is 400-10000, the hydroxyl value is 100-300mg KOH/g, the functionality of the polyether polyol is 2-4, the molecular weight is 400-10000, and the hydroxyl value is 100-300mg KOH/g.

6. The novel flame retardant low shrinkage polyurethane foam caulking agent according to claim 1, wherein the polyester polyol is a polyester containing an aromatic ring structure, and the functionality thereof is 2 to 3.

7. The novel flame retardant low shrink polyurethane foam caulk of claim 1 wherein the isocyanate is a polyphenylmethane polyisocyanate or toluene diisocyanate having a functionality of 2.2 to 2.9.

8. The novel flame retardant low shrink polyurethane foam underfill according to claim 1 wherein said catalyst is dimorpholinodiethyl ether.

9. The novel flame retardant low shrinkage polyurethane foam caulking agent of claim 1, wherein the foam stabilizer is polyethylene oxide and propylene oxide graft modified silane.

10. The novel flame retardant low shrinkage polyurethane foam caulking agent of claim 1, wherein the foaming agent is one or more of dimethyl ether, propane and butane, and 1,1,1, 2-tetrafluoroethane.

Technical Field

The invention relates to the technical field of polyurethane foam joint mixtures, and particularly belongs to a novel flame-retardant low-shrinkage polyurethane foam joint mixture.

Background

One-component polyurethane foam joint mixture (OCF for short) is a special moisture-curing rigid polyurethane foam system. Polyurethane prepolymer, catalyst, foaming agent, etc. are filled in a pressure-resistant aerosol can, and when the material is sprayed into holes or gaps from the can, the material is rapidly foamed and expanded and reacts with moisture in the air or on a substrate to be cured. The cured foam has multiple effects of caulking, bonding, sealing, heat insulation and the like. Because of its excellent caulking effect, OCF is an ideal caulking material, and has a wide application range and development prospect.

At present, the production of OCF almost adopts an in-tank polymerization production process, namely, firstly, filling polyol, catalyst, auxiliary agent and isocyanate into an aerosol tank, sealing a valve, then filling a foaming agent (propellant), and then fully shaking to ensure that materials in the tank are uniformly mixed and react to form a mixture of polyurethane prepolymer, auxiliary agent and propellant, thus obtaining a canned OCF product.

Because the single-component polyurethane foam is foamed twice, namely the polyurethane prepolymer is blown into foam by the propellant, and then the foam continuously reacts with the moisture in the air to generate CO₂Further expanding the foam, thereby finally forming a cured foam (15-30 kg/m) having a low density and a certain closed cell content³). Such low density polyurethane foams have a greater tendency to shrink as gas escapes from the foam. The magnitude of the shrinkage rate has a great influence on the filling and sealing effects. For example, when the OCF is used for sealing between a plastic-steel door window and a cement wall, if the shrinkage rate is too large, the foam and the wall are separated to form a gap, and a cold bridge or water leakage phenomenon of the wall is caused.

Polyurethane materials, like other organic polymers, are flammable polymers for the flame retardancy of the material. The polyurethane foam has low density and large specific surface, is easier to burn compared with non-foam materials, generates a large amount of toxic smoke after burning and decomposing, and has great threat to human life. Therefore, the flame retardant problem of polyurethane is very prominent. Many applications of polyurethane foams, such as building materials, mattresses, furniture, insulation materials, automotive seating and interior materials, etc., have flame retardant requirements. In the research of flame retardance, organic flame retardants or inorganic flame retardants containing elements such as chlorine, bromine, phosphorus, antimony, nitrogen, boron and the like are generally added into a production formula, and reactive flame retardants containing flame retardant elements can also be used as foam raw materials. The addition of the flame retardant improves the flame retardance of the foam, so that the combustion is delayed, the smoke is blocked, and even the ignition part is self-extinguished.

Most of the flame retardants applied most at present contain halogen, and because the materials of the halogen-containing flame retardants generate more toxic gases and generate more smoke during combustion, the halogen flame retardants are gradually eliminated worldwide. It is found that montmorillonite added into polymer body can not only prepare nanometer composite material with excellent performance, but also raise the size stability and fire resistance of the material, and is a filler with good cost performance. Current research on montmorillonite nanocomposites is also very intense.

Montmorillonite is a natural clay mineral, the basic structural unit is a layered structure formed by a sheet of aluminum-oxygen octahedron sandwiched between two sheets of silicon-oxygen tetrahedron and sharing oxygen atoms, and the structure of the mineral is 2: 1 layered silicate, namely, the mineral is derived from the sandwiched structure. The thickness of each lamella is about 1 nm; the length and width are each about 100 nm. The structure of montmorillonite endows it with special properties, and can be used for preparing nano composite materials in different forms.

Various methods for preparing polymer/montmorillonite nanocomposites are collectively referred to as intercalation compounding (intercalation compounding). The method is characterized in that a monomer or a polymer is inserted between layered silicate sheets treated by an intercalating agent in a liquid, melt or solution mode, so that the sheet structure of the silicate is destroyed, the silicate is stripped into a basic unit with the thickness of 1nm and uniformly dispersed in a polymer matrix, and the composition of a macromolecule and clay on a nanometer scale is realized.

Organic montmorillonite is used as filler and added into OCF, the filler is dispersed in polyester polyol or polyether polyol through violent shearing and stirring, the polyester polyol or polyether polyol and isocyanate are filled into an aerosol can, and then propellant is filled into the aerosol can to obtain polyurethane prepolymer.

Disclosure of Invention

The invention aims to provide a novel flame-retardant low-shrinkage polyurethane foam gap filler, which overcomes the defects of the prior art.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

novel flame retardant low shrinkage polyurethane foam caulking agent, comprising: the flame retardant comprises polyester polyol, polyether polyol, a catalyst, a flame retardant, a foam stabilizer, a foaming agent and isocyanate, wherein the flame retardant comprises a reactive flame retardant and an additive flame retardant.

Wherein the reactive flame retardant is one or more of trichloroisopropyl phosphate, chlorinated paraffin, tris (dipropylene glycol) phosphite, tris (polyoxyalkylene) phosphate, tris (polyoxyalkylene) phosphite, tris (cyanated polyol) phosphate dibromopentanediol polyether polyol solution, brominated pentaerythritol and tetrabromophthalic anhydride series flame retardant polyol, polyether Ixol B251 or polyether Ixol M125.

Wherein the additive flame retardant is one of organic montmorillonite, tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methyl phosphonate or polybrominated diphenyl ether.

Wherein, the pH value of the organic montmorillonite is 8-9.

Wherein, the functionality of the polyester polyol is 2-4, the molecular weight is 400-10000, the hydroxyl value is 100-300mgKOH/g, the functionality of the polyether polyol is 2-4, the molecular weight is 400-10000, and the hydroxyl value is 100-300 mgKOH/g.

Wherein the polyester polyol is a polyester containing an aromatic ring structure, and the functionality of the polyester polyol is 2-3.

Wherein the isocyanate is polyphenyl methane polyisocyanate or toluene diisocyanate with functionality of 2.2-2.9.

Wherein the catalyst is dimorpholinodiethylether.

Wherein the foam stabilizer is polyethylene oxide and propylene oxide graft modified silane.

Wherein, the foaming agent is one or more of dimethyl ether, propane and butane and 1,1,1, 2-tetrafluoroethane.

Compared with the prior art, the invention has the following implementation effects: the organic montmorillonite with alkalinity is used for modifying the gap filler, the montmorillonite not only plays a role in flame retardance, but also is alkaline after being treated by alkyl ammonia, so that toxic substances generated by a chlorine-containing flame retardant can be effectively neutralized and absorbed by the montmorillonite, and the toxicity generated by the chlorine-containing flame retardant is obviously reduced when the gap filler is used; in addition, the organic montmorillonite is added to support the matrix of the joint mixture, so that the shrinkage rate of foam generated when the joint mixture is used is reduced.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The polyester polyol adopts products which are sold in the market and are produced by STEPANOL COMPANY COMPANY and have the brands of polyester 3152, polyester 2412 and polyester 2352; polyether polyol is produced by Shanghai Gaoqiao petrochemical three plants, and the polyether polyol is the products of polyether-210 and polyether-310; polyphenylmethane polyisocyanate (p-MDI), Tolylene Diisocyanate (TDI) or modified products thereof having an isocyanate functionality of 2.2 to 2.9 may be commercially available products such as those manufactured by Huntsman CORP. company under the brand number SUP50OS, SUP2085, BASF CORP. company under the brand number M20S, BAYER CORP. company under the brand number 44V20L, and Nintentan Wanhua polyurethane company under the brand number PM-200; the montmorillonite is a commercial product, and the preparation method of the organic montmorillonite comprises the following steps: adding montmorillonite into solution containing alkylammonium (hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride or octadecyltrimethylammonium chloride), stirring, heating to 70 deg.C, reacting for 6 hr, vacuum filtering, and washing precipitate with deionized water until pH is 7, 8 or 9 to obtain organic montmorillonite; the foam stabilizer is selected from surfactants for polyurethane rigid foam or polyisocyanate foam, the foam stabilizer is polyethylene oxide and propylene oxide graft modified silane, and commercially available products can be adopted, such as products with the trade names of B8404, B8460 or B8462 produced by Germany Gausset company, such as products with the trade names of L-6900, L-5440, L-5420 and L-5421 produced by American Magi Charantia company, such as products with the trade names of DC5604, DC193 and DC5589 produced by American gas products company; ixol B251 and Ixol M125 are two types of flame retardant polyethers available from Solvay corporation.