阅读说明：本技术 一种改性酚醛树脂泡沫材料 (Modified phenolic resin foam material ) 是由 任进福 任凯 刘涛 陈建国 于 2020-05-18 设计创作，主要内容包括：本发明公开了一种改性酚醛树脂泡沫材料,其发泡原料的主要组成为热固性酚醛树脂、表面活性剂、发泡剂、酸固化剂和改性剂,改性剂为醚类化合物和/或热塑性酚醛树脂粉末,醚类化合物为乙二醇单乙醚和/或二乙二醇单丁醚。该改性酚醛树脂泡沫材料中的发泡原料中包含乙二醇单乙醚和/或二乙二醇单丁醚,发泡固化所得的泡沫体闭孔率高,导热系数低,并且闭孔结构稳定持久,有助于延长泡沫体的使用寿命,降低包含酚醛泡沫材料的产品维护成本,尤其适用于保温建筑材料以及空调管道材料等绝热要求高的产品。(The invention discloses a modified phenolic resin foam material, which mainly comprises a foaming raw material of thermosetting phenolic resin, a surfactant, a foaming agent, an acid curing agent and a modifier, wherein the modifier is an ether compound and/or thermoplastic phenolic resin powder, and the ether compound is ethylene glycol monoethyl ether and/or diethylene glycol monobutyl ether. The foaming raw materials in the modified phenolic resin foam material contain ethylene glycol monoethyl ether and/or diethylene glycol monobutyl ether, the foam obtained by foaming and curing has high closed cell rate and low heat conductivity coefficient, the closed cell structure is stable and durable, the service life of the foam is prolonged, the maintenance cost of the product containing the phenolic foam material is reduced, and the modified phenolic resin foam material is particularly suitable for products with high heat insulation requirements such as heat insulation building materials, air-conditioning pipeline materials and the like.)

1. The modified phenolic resin foam material is characterized in that the foaming raw materials mainly comprise thermosetting phenolic resin, a surfactant, a foaming agent, an acid curing agent and a modifier, wherein the modifier is an ether compound and/or thermoplastic phenolic resin powder, and the ether compound is ethylene glycol monoethyl ether and/or diethylene glycol monobutyl ether.

2. The modified phenolic resin foam material of claim 1, wherein the weight ratio of the thermosetting phenolic resin to the ether compound is 100: (1-30).

3. The modified phenolic resin foam material of claim 1, wherein the weight ratio of the thermosetting phenolic resin to the thermoplastic phenolic resin powder is 100: (0.5 to 8).

4. The modified phenolic resin foam material of claim 1, 2 or 3, wherein the modifier is a combination of an ether compound and a thermoplastic resin powder.

5. The modified phenolic resin foam material as claimed in claim 4, wherein the foaming raw material comprises, by weight, 100 parts of thermosetting phenolic resin, 2-6 parts of surfactant, 3-20 parts of foaming agent, 3-15 parts of ether compound, 1-5 parts of thermoplastic phenolic resin powder, and 10-30 parts of acid curing agent.

6. The modified phenolic resin foam material as claimed in claim 1 or 4, wherein the thermosetting phenolic resin is prepared by reacting phenol and formaldehyde under alkaline conditions; the molar ratio of phenol to formaldehyde is 1: (1.5-3.0); the thermosetting phenolic resin has a solid content of 75-85%, a water content of 3-10% and a viscosity of 2000-8000 mPa & s.

7. The modified phenolic resin foam material as claimed in claim 1, wherein the particle size of the thermoplastic phenolic resin powder is 300-1000 mesh.

8. The modified phenolic resin foam material as claimed in claim 1, wherein the composition of the foaming raw material further comprises urea, and the weight ratio of the thermosetting phenolic resin to the urea is 100: (2-10).

9. The modified phenolic resin foam material as claimed in claim 1, wherein the foaming temperature of the foaming raw material is 65-75 ℃, and the foaming curing time is 8-30 min.

10. The modified phenolic resin foam material as claimed in claim 1, wherein the density of the phenolic foam material is 20-100 kg/m³。

Technical Field

The invention relates to the technical field of phenolic foam materials, in particular to a modified phenolic resin foam material.

Background

The phenolic foam has a great practical value as a heat insulation material due to the excellent performances of low heat conductivity coefficient, light weight, flame retardance, low smoke generation, corrosion resistance, easy molding and processing and the like, and is widely applied to building external wall heat insulation, central air-conditioning ventilation pipelines and the like.

The foaming raw material component of the phenolic foam is as described in CN103694626A, and comprises phenolic resin, foaming agent, surfactant, curing agent or other additives. At present, the domestic phenolic foam board has two problems: firstly, the heat conductivity coefficient is high and is more than 0.030W/m.K; secondly, the closed pore structure in the phenolic foam enables the phenolic foam to have thermal insulation, but the pore structure is broken along with the prolonging of the service life of the foam, so that the thermal conductivity is increased, and the long-term stability of the thermal insulation performance of the existing phenolic foam is poor. Reducing the thermal conductivity and improving the long-term stability of the insulation effect are major technical problems to be solved urgently by technical personnel in the phenolic foam industry.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a modified phenolic resin foam material, wherein the obtained phenolic resin foam material has a closed cell structure with stable and durable structure.

In order to achieve the technical effects, the technical scheme of the invention is as follows: a modified phenolic resin foam material mainly comprises a foaming raw material of thermosetting phenolic resin, a surfactant, a foaming agent, an acid curing agent and a modifier, wherein the modifier is an ether compound and/or thermoplastic phenolic resin powder, and the ether compound is ethylene glycol monoethyl ether and/or diethylene glycol monobutyl ether.

The preferable technical scheme is that the weight ratio of the thermosetting phenolic resin to the ether compound is 100: (1-30). The thermal conductivity coefficient of the phenolic foam is not obviously improved when the addition amount of the ether compound is too small, and the foam performance is influenced when the addition amount is too large.

The preferable technical scheme is that the weight ratio of the thermosetting phenolic resin to the thermoplastic phenolic resin powder is 100: (0.5 to 8). The thermal conductivity coefficient of the phenolic foam is not obviously improved when the addition amount of the thermoplastic phenolic resin is too small, and the foam curing time is influenced when the addition amount is too large.

Preferably, the modifier is formed by combining an ether compound and thermoplastic resin powder. The simultaneous use of the two modifiers has a synergistic effect on improving the long-term stability of the closed cell structure of the phenolic resin foam.

The preferable technical scheme is that the foaming raw materials mainly comprise, by weight, 100 parts of thermosetting phenolic resin, 2-6 parts of surfactant, 3-20 parts of foaming agent, 3-15 parts of ether compound, 1-5 parts of thermoplastic phenolic resin powder and 10-30 parts of acid curing agent.

The preferable technical scheme is that the thermosetting phenolic resin is prepared by reacting phenol and formaldehyde under an alkaline condition; the molar ratio of phenol to formaldehyde is 1: (1.5-3.0); the thermosetting phenolic resin has a solid content of 75-85%, a water content of 3-10% and a viscosity of 2000-8000 mPa & s.

The preferable technical scheme is that the particle size of the thermoplastic phenolic resin powder is 300-1000 meshes. The particle size is too large or too small, and the compatibility of the powder with thermosetting phenol aldehyde is poor.

The preferable technical scheme is that the foaming raw material also comprises urea, and the weight ratio of the thermosetting phenolic resin to the urea is 100: (2-10).

The preferable technical scheme is that the foaming temperature of the foaming raw material is 65-75 ℃, and the foaming curing time is 8-30 min.

The preferable technical scheme is that the density of the phenolic foam material is 20-100 kg/m³。

The invention has the advantages and beneficial effects that:

the foaming raw materials in the modified phenolic resin foam material contain ethylene glycol monoethyl ether and/or diethylene glycol monobutyl ether, the foam obtained by foaming and curing has high closed cell rate and low heat conductivity coefficient, the closed cell structure is stable and durable, the service life of the foam is prolonged, the maintenance cost of the product containing the phenolic foam material is reduced, and the modified phenolic resin foam material is particularly suitable for products with high heat insulation requirements such as heat insulation building materials, air-conditioning pipeline materials and the like.

Detailed Description

The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.

The basic composition of the foaming raw material comprises thermosetting phenolic resin, a surfactant, a foaming agent and an acid curing agent, wherein:

the surfactant is used for reducing the interfacial tension between the phenolic resin and each raw material component, so that each component such as a foaming agent and the like can be fully and uniformly mixed in the liquid phase phenolic resin, and uniform foam can be obtained. The surfactant is selected from nonionic surfactants, including but not limited to fatty alcohol-polyoxyethylene ether surfactants, silicone compounds containing polyoxyethylene ether.

Blowing agents include physical blowing agents and chemical blowing agents, wherein blowing agents that are liquid at ambient temperatures are more readily dispersed in phenolic resins, including but not limited to trichlorofluoromethane, trichlorotrifluoroethane, cyclopentane, ammonium carbonates, bicarbonates. The preferred blowing agent is one or a combination of two or more selected from cyclopentane and fluorine-substituted olefin blowing agents based on a foaming raw material containing ethylene glycol monoethyl ether and/or diethylene glycol monobutyl ether.

The urea in the foaming raw material can ensure that the foam holes of the foaming product are small, compact and uniform, the closed hole rate is high, and the reduction of the heat conduction value is facilitated.

The acid curing agent may be selected from a range including inorganic acids and organic acids, and a combination of inorganic acids and organic acids may be used. The acid curing agent is preferably at least one selected from the group consisting of p-toluenesulfonic acid and phenolsulfonic acid, and further, the mixing ratio of the two organic acids is preferably 7: 3. The p-toluenesulfonic acid and phenolsulfonic acid are added by first dissolving in a lower alcohol such as ethanol, ethylene glycol and mixing with a mixture of the other components of the foaming raw material except the acid curing agent.

The foaming raw material can also be added with known components used in the phenolic foam material foaming raw material, such as an anticorrosive agent, a reinforcing agent, a plasticizer, a flame retardant and the like according to needs so as to achieve corresponding known effects.