阅读说明：本技术 一种发泡用酚醛树脂、发泡材料及其制备方法和应用 (Phenolic resin for foaming, foaming material, and preparation method and application thereof ) 是由 施晓旦 孙海强 赵吉 于 2020-04-21 设计创作，主要内容包括：本发明公开了一种发泡用酚醛树脂、发泡材料及其制备方法和应用。发泡用酚醛树脂的原料组合物包括下述组分：1份苯酚、0.01～10.5份改性生物提取物、0.1～10份多聚甲醛、0.01～10份碱性催化剂和0.01～3份水；其中,改性生物提取物的制备方法为：生物提取物和亚硫酸钠经磺化反应,干燥,即可；亚硫酸钠与生物提取物的质量比为(0.1～0.7)：1；磺化反应的温度为70～145℃。本发明中发泡用酚醛树脂的原料采用改性后的生物提取物,可有效提高反应活性；改性生物提取物无毒无害,价格低廉,提高资源利用率；制备发泡材料过程中甲醛释放量降低；并且合成出的发泡材料柔韧性佳,压缩强度和弯曲断裂力均较高。(The invention discloses phenolic resin for foaming, a foaming material, and a preparation method and application thereof. The raw material composition of the phenolic resin for foaming comprises the following components: 1 part of phenol, 0.01-10.5 parts of modified biological extract, 0.1-10 parts of paraformaldehyde, 0.01-10 parts of alkaline catalyst and 0.01-3 parts of water; the preparation method of the modified biological extract comprises the following steps: performing sulfonation reaction on the biological extract and sodium sulfite, and drying; the mass ratio of the sodium sulfite to the biological extract is (0.1-0.7): 1; the temperature of the sulfonation reaction is 70-145 ℃. The raw material of the phenolic resin for foaming adopts the modified biological extract, so that the reaction activity can be effectively improved; the modified biological extract is non-toxic and harmless, has low price and improves the utilization rate of resources; the formaldehyde emission in the process of preparing the foaming material is reduced; and the synthesized foaming material has good flexibility, high compressive strength and high bending breaking force.)

1. A raw material composition of phenolic resin for foaming is characterized by comprising the following components: 1 part of phenol, 0.01-10.5 parts of modified biological extract, 0.1-10 parts of paraformaldehyde, 0.01-10 parts of alkaline catalyst and 0.01-3 parts of water;

the preparation method of the modified biological extract comprises the following steps: performing sulfonation reaction on the biological extract and sodium sulfite, and drying; the mass ratio of the sodium sulfite to the biological extract is (0.1-0.7): 1; the temperature of the sulfonation reaction is 70-145 ℃.

2. A raw material composition of phenolic resin for foaming according to claim 1, wherein in the preparation method of the modified biological extract, the solid content of the biological extract is 20% to 80%, preferably 50%;

and/or in the preparation method of the modified biological extract, the mass ratio of the sodium sulfite to the biological extract is (0.3-0.7): 1, preferably (0.4 to 0.7): 1;

and/or in the preparation method of the modified biological extract, the temperature of the sulfonation reaction is 100-145 ℃;

and/or in the preparation method of the modified biological extract, the sulfonation reaction time is 40-130 min, preferably 90-120 min;

and/or in the preparation method of the modified biological extract, the biological extract is paper-making waste generated in the process of preparing wood pulp, and preferably is one or more of rotten pulp, pulp residue, bark, medicament waste liquid, grass powder, siliceous white mud and pulping waste liquid;

preferably, the wood pulp is prepared by a caustic or sulfate process, more preferably a sulfate process;

preferably, the preparation method of the biological extract comprises the following steps: cooking wood chips, a sodium hydroxide aqueous solution with the concentration of 0.5-1.5 mol/L and a sodium sulfide aqueous solution with the concentration of 0.1-0.3 mol/L, spraying, recovering steam, washing to obtain sulfuric acid paper pulp, and removing the sulfuric acid paper pulp to obtain a residual material which is the biological extract; the cooking temperature is 160-180 ℃, and the cooking time is 80-100 min; more preferably, the preparation method of the biological extract comprises the following steps: cooking wood chips, a sodium hydroxide aqueous solution with the concentration of 1mol/L and a sodium sulfide aqueous solution with the concentration of 0.2mol/L, blowing, recovering steam, washing to obtain sulfuric acid pulp, and removing the sulfuric acid pulp to obtain the residual material which is the biological extract; the cooking temperature is 170 ℃, and the cooking time is 90 min.

3. The raw material composition of phenolic resin for foaming according to claim 1, wherein the solid content of the modified biological extract is equal to or greater than 95%, preferably 95% to 98%, more preferably 96%;

and/or, the alkaline catalyst is one or more of sodium hydroxide, barium hydroxide and calcium hydroxide, preferably any one of sodium hydroxide, barium hydroxide and calcium hydroxide;

and/or, the weight part of the modified biological extract is 0.04-10 parts, preferably 0.5-10 parts;

and/or the weight portion of the paraformaldehyde is 0.4-10 parts, preferably 0.65-10 parts;

and/or, the weight part of the basic catalyst is 0.04-10 parts, preferably 0.25-10 parts;

and/or the water accounts for 0.04-3 parts by weight, preferably 0.15-3 parts by weight;

preferably, the raw material composition of the phenolic resin for foaming consists of the following components: 1 part of phenol, 0.01-10.5 parts of modified biological extract, 0.1-10 parts of paraformaldehyde, 0.01-10 parts of alkaline catalyst and 0.01-3 parts of water.

4. A method for preparing a phenolic resin for foaming, which is characterized in that the raw material in the method for preparing the phenolic resin for foaming is the raw material composition of the phenolic resin for foaming as described in any one of claims 1 to 3, and the method specifically comprises the following steps:

(1) mixing phenol and an alkaline catalyst for reaction to prepare a material A;

(2) mixing the material A with paraformaldehyde for reaction to obtain a material B;

(3) mixing the material B, a catalyst, the modified biological extract and water for reaction to prepare a material C;

(4) and mixing the material C, paraformaldehyde and a catalyst for reaction, cooling, and adjusting the pH value to 6.0-7.5.

5. The method for preparing phenolic resin for foaming according to claim 4, wherein in the step (1), the temperature of the mixing reaction is 45 to 85 ℃, preferably 50 to 80 ℃, and more preferably 60 ℃;

and/or, in the step (1), the mixing reaction time is 10-40 min, preferably 30 min;

and/or, in the step (1), the weight part of the alkaline substance is 0.016-4 parts, preferably 0.1-4 parts, based on 1 part of the phenol;

and/or, in the step (2), the temperature of the mixing reaction is 45-85 ℃, preferably 50-80 ℃, and more preferably 60 ℃;

and/or, in the step (2), the mixing reaction time is 25-60 min, preferably 30 min;

and/or in the step (2), the weight part of the paraformaldehyde is 0.24-6 parts, preferably 0.35 part, based on 1 part of the phenol.

6. The method for preparing phenolic resin for foaming according to claim 4, wherein in the step (3), the temperature of the mixing reaction is 55 to 95 ℃, preferably 60 to 90 ℃, and more preferably 75 ℃;

and/or, in the step (3), the mixing reaction time is 30-100 min, preferably 50 min;

and/or, in the step (3), the weight part of the catalyst is 0.016-4 parts, preferably 0.1-4 parts, based on 1 part of the phenol;

and/or, in the step (3), the weight part of the modified biological extract is 0.04-10 parts, preferably 0.5-10 parts, based on 1 part by weight of the phenol;

and/or in the step (3), the weight part of the water is 0.04-3 parts, preferably 0.15-3 parts, based on 1 part of the phenol;

and/or in the step (4), the temperature of the mixing reaction is 80-120 ℃, preferably 80-100 ℃;

and/or, in the step (4), the mixing reaction time is 60-150 min, preferably 90 min;

and/or, in the step (4), the temperature is reduced to 45-55 ℃, preferably to 50 ℃;

and/or, in the step (4), the pH is adjusted to 6.0-7.5 by using an acidic substance, preferably to 6.5-7.0 by using an acidic substance; preferably, the acidic substance is one or more of hydrochloric acid, acetic acid and formic acid, more preferably any one of hydrochloric acid with a mass percentage of 20-35%, an acetic acid aqueous solution with a mass percentage of 20-35% and a formic acid aqueous solution with a mass percentage of 20-35%, and even more preferably any one of hydrochloric acid with a mass percentage of 30%, an acetic acid aqueous solution with a mass percentage of 30% and a formic acid aqueous solution with a mass percentage of 30%;

and/or in the step (4), after the pH is adjusted to 6.0-7.5, further cooling is carried out; preferably, the cooling is to room temperature, more preferably to 25 ℃;

and/or in the step (4), the weight part of the paraformaldehyde is 0.16-4 parts, preferably 0.3-4 parts, based on 1 part of the phenol;

and/or, in the step (4), the weight part of the catalyst is 0.008 to 2 parts, preferably 0.05 to 2 parts, based on 1 part of the phenol.

7. A phenolic resin for foaming produced by the method for producing a phenolic resin for foaming according to any one of claims 4 to 6.

8. Use of the phenolic resin for foaming according to claim 7 as a raw material in the preparation of a foamed material.

9. A foamed material obtained by curing the phenolic resin for foaming according to claim 7, a curing agent, a surfactant and a foaming agent.

10. The foamed material of claim 9, wherein the curing agent is oxalic acid;

and/or, the surfactant is tween-80;

and/or the foaming agent is n-pentane;

and/or the weight part ratio of the phenolic resin for foaming to the curing agent is 100: (4-10), preferably 100: 5;

and/or the weight part ratio of the phenolic resin for foaming to the surfactant is 100: (3-9), preferably 100: 6;

and/or the weight part ratio of the phenolic resin for foaming to the foaming agent is 100: (3-12), preferably 100: 6;

and/or the curing temperature is 55-75 ℃, preferably 60-75 ℃;

and/or the curing time is 10-25 min, preferably 10-15 min.

Technical Field

The invention relates to phenolic resin for foaming, a foaming material, and a preparation method and application thereof.

Background

The phenolic foam plastic is named as the third generation new heat-insulating material or the heat-insulating king because the phenolic foam plastic has good flame resistance, low smoke, good high temperature resistance, stable performance, heat insulation, sound insulation, easy molding and processing and better durability. The low toxicity and flame retardance are excellent properties of phenolic resin foam, which causes the rapid development of technical development. Meanwhile, the traditional phenolic foam has great problems, such as the existing phenolic foam has large brittleness, poor strength and toughness, is easy to fall off in the using process, and is easy to fall off when drilling and cutting. In addition, the phenolic resin used for foaming has a large content of free monomers, so that the phenolic foam has a large smell and can affect the environment and human body to a certain extent in the processing and application processes. These disadvantages limit the use of phenolic foams.

With the increasing enhancement of human environmental awareness and resource crisis, how to effectively and comprehensively utilize biomass resources to replace petrochemical raw materials has become an increasingly hot topic and research direction.

Therefore, the development of a phenolic resin for foaming, which has the advantages of non-toxic and harmless raw materials, wide sources, low content of free aldehyde in the using process and good mechanical properties, is urgently needed in the field.

Disclosure of Invention

The invention aims to solve the technical problems of high free aldehyde, high brittleness, low strength and the like of phenolic foam in the prior art in the using process, and provides phenolic resin for foaming, a foaming material, a preparation method and application thereof. The raw material of the phenolic resin for foaming adopts the modified biological extract, so that the reaction activity can be effectively improved; the modified biological extract is made of wood, is non-toxic and harmless, has low price, realizes waste utilization, and improves the resource utilization rate; the phenolic resin for foaming synthesized by the invention has full reaction among monomers in the process of preparing the foaming material, and the formaldehyde emission is greatly reduced; and the synthesized foaming material has good flexibility, high compressive strength and high bending breaking force.

The inventor finds that a sulfonation group can be grafted on a molecular chain of the biological extract through sulfonation reaction, so that the reaction activity can be effectively improved; the synthesized foaming material contains sulfonate groups, and the flexibility, the compressive strength and the bending breaking force of the foaming material are improved.

The invention adopts the following technical scheme to solve the technical problems:

the invention provides a raw material composition of phenolic resin for foaming, which comprises the following components: 1 part of phenol, 0.01-10.5 parts of modified biological extract, 0.1-10 parts of paraformaldehyde, 0.01-10 parts of alkaline catalyst and 0.01-3 parts of water;

the preparation method of the modified biological extract comprises the following steps: performing sulfonation reaction on the biological extract and sodium sulfite, and drying; the mass ratio of the sodium sulfite to the biological extract is (0.1-0.7): 1; the temperature of the sulfonation reaction is 70-145 ℃.

In the preparation method of the modified biological extract, the solid content of the biological extract can be the conventional solid content of papermaking waste generated in the process of preparing wood pulp in the field, and is preferably 20-80%, and more preferably 50%. In the present invention, the solid content of the biological extract generally refers to the mass percentage of the dry material of the biological extract after the solvent is removed.

In the preparation method of the modified biological extract, the mass ratio of the sodium sulfite to the biological extract is preferably (0.3-0.7): 1, more preferably (0.4 to 0.7): 1. during the development process, the inventor finds that when the using amount of sodium sulfite is less than 0.1: 1, the sulfonation degree is not enough, the molecular chain of the biological extract is not stretched in time during foaming, and holes are left in the incompletely sulfonated part after foaming forming, so that the compression strength and the bending breaking force are influenced; when the amount of sodium sulfite is higher than 0.7: 1, since the component is an inorganic salt, the salt crystals are present in the foam during foaming, and the bending breaking force is affected during detection.

In the preparation method of the modified biological extract, the temperature of the sulfonation reaction is preferably 100-145 ℃. The inventor finds that when the temperature of sulfonation reaction is lower than 70 ℃, the sulfonation degree of the biological extract is not enough, the molecular chain of the biological extract is not stretched in time during foaming, and holes are left in the incompletely sulfonated part after foaming forming, so that the compression strength and the bending breaking force are influenced; when the temperature is higher than 145 ℃, the biological extract is cracked, cannot play a role in enhancing during foaming, and influences the application performance.

In the preparation method of the modified biological extract, the sulfonation reaction time can be the time conventionally used in the operation in the field, preferably 40-130 min, and more preferably 90-120 min.

In the preparation method of the modified biological extract, the drying conditions and method can be the conditions and methods conventional in the operation in the field.

In the preparation method of the modified biological extract, the biological extract can be paper-making waste generated in the process of preparing wood pulp in the field, and generally can be one or more of rotten pulp, pulp residue, bark, medicament waste liquid, grass powder, siliceous white mud and pulping waste liquid, such as biological extract provided by Jiningmingshi New materials Co.

The preparation method of the wood pulp can be a conventional method in the field, and can be a caustic soda method or a sulfate method generally, and the sulfate method is preferred.

In a preferred embodiment, the method of preparing the biological extract comprises the steps of: cooking wood chips, a sodium hydroxide aqueous solution with the concentration of 0.5-1.5 mol/L and a sodium sulfide aqueous solution with the concentration of 0.1-0.3 mol/L, spraying, recovering steam, washing to obtain sulfuric acid paper pulp, and removing the sulfuric acid paper pulp to obtain a residual material which is the biological extract; the cooking temperature is 160-180 ℃, and the cooking time is 80-100 min.

In a more preferred embodiment, the method of preparing the biological extract comprises the steps of: cooking wood chips, a sodium hydroxide aqueous solution with the concentration of 1mol/L and a sodium sulfide aqueous solution with the concentration of 0.2mol/L, blowing, recovering steam, washing to obtain sulfuric acid pulp, and removing the sulfuric acid pulp to obtain the residual material which is the biological extract; the cooking temperature is 170 ℃, and the cooking time is 90 min.

In the present invention, the solid content of the modified biological extract may be ≧ 95%, preferably 95% to 98%, for example 96%.

In the present invention, the basic catalyst may be one conventionally used in the art, preferably one or more of sodium hydroxide, barium hydroxide and calcium hydroxide, more preferably any one of sodium hydroxide, barium hydroxide and calcium hydroxide.

In the present invention, the weight portion of the modified biological extract is preferably 0.04 to 10, and more preferably 0.5 to 10.

In the present invention, the weight portion of the paraformaldehyde is preferably 0.4 to 10 parts, and more preferably 0.65 to 10 parts.

In the present invention, the weight portion of the basic catalyst is preferably 0.04 to 10 parts, and more preferably 0.25 to 10 parts.

In the present invention, the weight part of the water is preferably 0.04 to 3 parts, more preferably 0.15 to 3 parts.

In a preferred embodiment, the raw material composition of the phenolic resin for foaming is composed of the following components: 1 part of phenol, 0.01-10.5 parts of modified biological extract, 0.1-10 parts of paraformaldehyde, 0.01-10 parts of alkaline catalyst and 0.01-3 parts of water.

The invention also provides a preparation method of the phenolic resin for foaming, which takes the raw material composition of the phenolic resin for foaming as the raw material and specifically comprises the following steps:

(1) mixing phenol and an alkaline catalyst for reaction to prepare a material A;

(2) mixing the material A with paraformaldehyde for reaction to obtain a material B;

(3) mixing the material B, a catalyst, the modified biological extract and water for reaction to prepare a material C;

(4) and mixing the material C, paraformaldehyde and a catalyst for reaction, cooling, and adjusting the pH value to 6.0-7.5.

In step (1), the temperature of the mixing reaction may be a conventional temperature in the operation in the field, preferably 45 to 85 ℃, more preferably 50 to 80 ℃, for example 60 ℃.

In the step (1), the mixing reaction time may be conventional time in the field, preferably 10-40 min, and more preferably 30 min.

In the step (1), the weight part of the alkaline substance is 1 part of the phenol, and may be the weight part of the phenol conventionally used in the reaction in the field, preferably 0.016-4 parts, more preferably 0.1-4 parts.

In the step (2), the temperature of the mixing reaction may be a conventional temperature in the operation in the field, preferably 45 to 85 ℃, more preferably 50 to 80 ℃, for example 60 ℃.

In the step (2), the time of the mixing reaction may be the conventional time in the operation in the field, preferably 25 to 60min, and more preferably 30 min.

In the step (2), the weight part of the paraformaldehyde is 1 part by weight of the phenol, which is a weight part conventionally used in the reaction in the field, preferably 0.24 to 6 parts by weight, and more preferably 0.35 part by weight.

In step (3), the temperature of the mixing reaction may be a conventional temperature in the art, preferably 55 to 95 ℃, more preferably 60 to 90 ℃, for example 75 ℃.

In the step (3), the time of the mixing reaction may be the conventional time in the operation in the field, preferably 30 to 100min, and more preferably 50 min.

In the step (3), the weight part of the catalyst is 1 part by weight of the phenol, and may be the weight part of the phenol conventionally used in the reaction in the field, preferably 0.016-4 parts, more preferably 0.1-4 parts.

In the step (3), the weight part of the modified biological extract is 1 part by weight of the phenol, and may be the weight part of the phenol conventionally used in the reaction in the field, preferably 0.04 to 10 parts by weight, and more preferably 0.5 to 10 parts by weight.

In the step (3), the weight part of the water is 1 part of the phenol, and may be the weight part of the phenol conventionally used in the reaction in the field, preferably 0.04 to 3 parts, and more preferably 0.15 to 3 parts.

In the step (4), the temperature of the mixing reaction may be a conventional temperature in the operation in the field, preferably 80 to 120 ℃, and more preferably 80 to 100 ℃.

In the step (4), the time of the mixing reaction may be the conventional time in the operation in the field, preferably 60 to 150min, and more preferably 90 min.

In the step (4), the temperature reduction condition and method may be conventional conditions and methods in the operation in the field, preferably, the temperature is reduced to 45-55 ℃, and more preferably, to 50 ℃.

In the step (4), the condition and method for adjusting pH may be conventional conditions and methods in the operation in the field, preferably, the pH is adjusted to 6.0 to 7.5 by using an acidic substance, and more preferably, the pH is adjusted to 6.5 to 7.0 by using an acidic substance.

The acidic substance may be one or more of hydrochloric acid, acetic acid and formic acid, preferably any one of hydrochloric acid with a mass percentage of 20-35%, an aqueous acetic acid solution with a mass percentage of 20-35% and an aqueous formic acid solution with a mass percentage of 20-35%, for example, any one of hydrochloric acid with a mass percentage of 30%, an aqueous acetic acid solution with a mass percentage of 30% and an aqueous formic acid solution with a mass percentage of 30%.

In the step (4), after the pH value is adjusted to 6.0-7.5, the operation of cooling is further included.

The cooling conditions and method may be conventional in the art for such operations, preferably cooling to room temperature, e.g. 25 ℃.

In the step (4), the weight part of the paraformaldehyde is 1 part by weight of the phenol, and is a weight part which is conventionally used in the reaction in this kind of field, preferably 0.16 to 4 parts by weight, and more preferably 0.3 to 4 parts by weight.

In the step (4), the weight part of the catalyst may be the weight part of the phenol of 1 part, preferably 0.008 to 2 parts, and more preferably 0.05 to 2 parts, which is a part conventionally used in the reaction in this field.

The invention also provides the phenolic resin for foaming prepared by the preparation method of the phenolic resin for foaming.

The invention also provides an application of the phenolic resin for foaming as a raw material in preparation of a foaming material.

The invention also provides a foaming material which is prepared by curing the phenolic resin for foaming, the curing agent, the surfactant and the foaming agent.

Among them, the curing agent may be one conventionally used in such reactions in the art, preferably oxalic acid.

The surfactant can be a surfactant conventionally used in this type of reaction in the field, and preferably is tween-80.

The blowing agent may be a blowing agent conventionally used in such reactions in the art, preferably n-pentane.

The weight part ratio of the phenolic resin for foaming and the curing agent can be conventional in the field, and is preferably 100: (4-10), more preferably 100: 5.

the weight part ratio of the phenolic resin for foaming and the surfactant can be conventional in the field, and is preferably 100: (3-9), more preferably 100: 6.

the weight part ratio of the phenolic resin for foaming and the foaming agent can be conventional in the field, and is preferably 100: (3-12), more preferably 100: 6.

the curing temperature may be a temperature conventional in the art, and is preferably 55 ℃ to 75 ℃, more preferably 60 ℃ to 75 ℃.

The curing time can be the time conventionally used in the art, preferably 10-25 min, and more preferably 10-15 min.

In the present invention, the room temperature may be generally 10 to 40 ℃.

On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows: the biological extract used in the invention is obtained from wood, belongs to a nontoxic and harmless product, has low price, realizes waste utilization, and improves the resource utilization rate; the amount of the used polyformaldehyde is relatively small, the monomers of the phenolic resin for foaming synthesized by the method react fully in the process of preparing the foaming material, the formaldehyde release amount is greatly reduced during foaming, and the mechanical properties such as flexibility, compressive strength, bending breaking force and the like are excellent; the biological extract partially replaces phenol, and can effectively relieve the current situation of shortage of fossil raw materials.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The biological extract used in the following examples was provided by Jinmingshi New materials, Inc., and had a solid content of 50%. The biological extract is papermaking waste generated in the process of preparing paper pulp by a sulfate method, and the preparation method specifically comprises the following steps: adding wood chips, a sodium hydroxide aqueous solution with the concentration of 1mol/L and a sodium sulfide aqueous solution with the concentration of 0.2mol/L into a digester, keeping the temperature at 170 ℃ for 90min, blowing the digested slurry, recovering steam, washing to obtain sulfuric acid paper pulp, and removing the sulfuric acid paper pulp to obtain a residual material which is a biological extract.