阅读说明：本技术 一种氨基酸改性烷基酚-甲醛树脂及其制备方法 (Amino acid modified alkylphenol-formaldehyde resin and preparation method thereof ) 是由 杜孟成 李庆朝 黄存影 李剑波 宋彦哲 师利龙 于 2019-11-27 设计创作，主要内容包括：本发明提供了一种氨基酸改性烷基酚-甲醛树脂,本发明还提供了上述氨基酸改性烷基酚-甲醛树脂的制备方法,本发明中不但避免了DL混合型氨基酸复杂的分离工艺,改性后的烷基酚-甲醛树脂具有极强的增粘性能,其增粘的持久性和湿热粘性性能优越。本发明还具有以下优势：原料使用时,具有使用固体甲醛的条件,从而替代部分甲醛水溶液,大幅度减少了废水量；选用氨基酸改性烷基酚-甲醛树脂,可以大幅度提高产品的可支化度,提高树脂的增粘性能；氨基酸不仅含有氨基、羧基、长链烷烃官能团,可以有效提高树脂与胶料的相溶性,降低迁移率,从而提高胶片的持久粘性。(The invention provides an amino acid modified alkylphenol-formaldehyde resin and a preparation method thereof, which not only avoids the complex separation process of DL mixed amino acid, but also has strong tackifying performance, and the tackifying durability and the hot and humid adhesive performance are excellent. The invention also has the following advantages: when the raw materials are used, the conditions of using solid formaldehyde are provided, so that part of formaldehyde aqueous solution is replaced, and the amount of wastewater is greatly reduced; the amino acid modified alkylphenol-formaldehyde resin is selected, so that the branching degree of the product can be greatly improved, and the tackifying performance of the resin is improved; the amino acid not only contains amino, carboxyl and long paraffin functional groups, but also can effectively improve the intermiscibility of the resin and the rubber material and reduce the mobility, thereby improving the lasting viscosity of the film.)

1. An amino acid modified alkylphenol-formaldehyde resin is characterized in that the structural formula is as follows:

the molecular weight is 1500-2000;

r' is amino acid structural formula

2. The amino acid-modified alkylphenol-formaldehyde resin as claimed in claim 1, wherein the amino acid is any one or a combination of 8 structural formulas:

3. the amino acid-modified alkylphenol-formaldehyde resin of claim 2, characterized in that the amino acid isComprises the following steps:

4. the amino acid-modified alkylphenol-formaldehyde resin as claimed in claim 1, wherein R is one of tert-butyl group and tert-octyl group; the structural formula of the tert-octyl is as follows:

the structural formula of the tertiary butyl group is:

5. a method for producing an amino acid-modified alkylphenol-formaldehyde resin according to claim 1, characterized by comprising the steps of:

step 1: mixing alkylphenol and a catalyst in a reaction container, heating to 90-98 ℃, then dripping formaldehyde aqueous solution, and carrying out reflux reaction for 1-3 h;

step 2: after the reaction in the step 1 is finished, adding amino acid for modification at the temperature of 90-100 ℃, and after the reaction is carried out for 1h, starting distillation; distilling water in the system, adding solid formaldehyde, and carrying out reflux reaction at the temperature of 80-100 ℃ for 1-3 h; then adding liquid alkali, and adjusting the pH to 7; obtaining an amino acid modified alkylphenol-formaldehyde resin intermediate;

and step 3: heating the amino acid modified alkylphenol-formaldehyde resin intermediate to 100-120 ℃, distilling out most of water in the system, heating to 150-160 ℃, and steaming out residual water and unreacted monomers in a vacuum state to obtain the amino acid modified alkylphenol-formaldehyde resin.

6. The method of claim 5, wherein the catalyst is an organic or inorganic acid, and the amount of the catalyst is 0.2-1.0% by mass of the alkylphenol.

7. The method for producing an amino acid-modified alkylphenol-formaldehyde resin according to claim 6, characterized in that the catalyst is p-toluenesulfonic acid, hydrochloric acid or sulfuric acid; the alkylphenol is one or more of p-tert-octylphenol and p-tert-butylphenol; wherein the structural formula of the p-tert-octylphenol is as follows:

the structural formula of the p-tert-butylphenol is as follows:

8. the method for producing an amino acid-modified alkylphenol-formaldehyde resin according to claim 6, characterized in that the concentration of the aqueous formaldehyde solution in step 1 is 30 to 40 wt%; the solid formaldehyde in the step 2 is paraformaldehyde or trioxymethylene; in the step 1, the dosage of the formaldehyde aqueous solution is 60-80% of the total mole number of formaldehyde.

9. The method for producing an amino acid-modified alkylphenol-formaldehyde resin according to claim 6, characterized in that the molar ratio of the added amount of the alkylphenol to the formaldehyde is 1.0: 0.7-1.0:1.2, and the mass ratio of the addition amount of the alkylphenol to the amino acid is 1.0: 0.05-0.10.

10. The method of claim 6, wherein the molar ratio of the added amount of the alkylphenol to the formaldehyde is 1.0: 0.9-1.0: 0.95; the mass ratio of the addition amount of the alkylphenol to the amino acid is 1: 0.07-0.10.

Technical Field

The invention belongs to the technical field of tackifying resins, and particularly belongs to an amino acid modified alkylphenol-formaldehyde resin and a preparation method thereof.

Background

The radial tire is commonly called as a steel tire, which is a novel tire with tire body cords arranged in the radial direction and a tire body tightly hooped by buffer layers arranged in the circumferential direction or close to the circumferential direction, and the adhesive strength of rubber and steel wires in the tire greatly influences the quality of the radial tire. Rubber self-adhesion is therefore important in the molding process and is therefore also referred to as molding tack; furthermore, if there is a lack of adhesion between the compounds, especially in the case of synthetic rubber compounds, the semi-finished part creeps to deform dimensionally, and the finished tire may experience a separation of the part from the part due to expansion during molding. In the design of all-steel radial tire products, a plurality of parts such as tire bead parts, belt ply edges and the like use thin rubber sheets with better viscosity, and if the phenomenon of non-sticking occurs, air is trapped in a tire blank during molding, so that the quality of a finished product is influenced.

Synthetic rubbers are widely used, have abrasion resistance, aging resistance and other special advantages, but lack sufficient self-adhesiveness, which causes difficulties in molding processes, and one of the common solutions is to add tackifying resins to improve the adhesiveness. The tackifying resin should have the following four conditions: (1) the compatibility with the rubber matrix is good; (2) the adhesive has strong adhesiveness; (3) the tackifying effect is durable and the change along with the time is small; (4) the vulcanization speed and the physical properties of the vulcanized rubber are not reduced.

The synthetic resin has better initial viscosity and durability, is more and more applied by tackifying resin, wherein the alkyl phenolic resin has the most excellent effect and is one of the main rubber auxiliary agent varieties for tire molding. However, the alkylphenol formaldehyde resin does not have outstanding storage viscosity and excellent wet heat adhesiveness, and cannot meet the production requirements of high-grade tires and rubber products. At present, some manufacturers of high-grade tires select an imported super tackifying resin (p-tert butyl phenol-acetylene resin), and the production process is extremely complex and the manufacturing cost is high. Therefore, tackifying resins with good performance and low cost become a research hotspot of rubber auxiliary related industries.

Chinese patent document CN102432787A, which has made some efforts to improve the durability and hot and humid tack of resin tackifying, discloses a modified hydrocarbylphenol-aldehyde resin used as a tackifier and a rubber composition containing the same, wherein a primary or secondary amine is used to improve the tack of the hydrocarbylphenol-aldehyde resin, and the amine used may be a saturated, unsaturated, aromatic, heterocyclic amine such as ethylamine, ethylenediamine, dimethylamine, imidazole, piperidine, pyrrole, and the like, and most preferably morpholine. Tests prove that the viscosity increasing durability of the modified alkyl phenolic resin is improved.

In the field of epoxy resin modification, amino acids are used to modify epoxy resins to achieve better performance. Amino acids are organic molecules having both amino, carboxyl and R groups, and the structural formula is shown below:

according to the nature of the R group, the amino acid can be classified into hydrophilic amino acid and hydrophobic amino acid. Hydrophobic amino acids if the R group on the amino acid is aliphatic, aromatic or sulfur-containing; and if the R group on the amino acid is a polar group, the amino acid is hydrophilic.

On the basis of the prior achievement, the related industries of the rubber auxiliary agents are continuously innovated.

Disclosure of Invention

The invention provides an amino acid modified alkylphenol-formaldehyde resin which has higher viscosity, and particularly, the durability and the damp-heat viscosity of tackifying are obviously improved.

Meanwhile, the invention also provides a preparation method of the amino acid modified alkylphenol-formaldehyde resin.

An amino acid modified alkylphenol-formaldehyde resin, which has the following structural formula:

the molecular weight is 1500-2000.

The amino acid-modified alkylphenolR' in the structural formula of the formaldehyde resin is an amino acid structural formula

In (1)And (5) structure.

Preferably, the amino acid is any one or more combination of the following 8 structural formulas:

preferably, the amino acids are:

preferably, in the structural formula of the amino acid modified alkylphenol-formaldehyde resin, R is one of tert-octyl and tert-butyl; the structural formula of the tert-octyl is as follows:

the structural formula of the tertiary butyl group is:

the preparation method of the amino acid modified alkylphenol-formaldehyde resin is characterized by comprising the following steps:

step 1: mixing alkylphenol and a catalyst in a reaction container, heating to 90-98 ℃, then dripping formaldehyde aqueous solution, and carrying out reflux reaction for 1-3 h;

step 2: after the reaction in the step 1 is finished, adding amino acid for modification at the temperature of 90-100 ℃, and after the reaction is carried out for 1h, starting distillation; distilling water in the system, adding solid formaldehyde, and carrying out reflux reaction at the temperature of 80-100 ℃ for 1-3 h; then adding liquid alkali, and adjusting the pH to 7; obtaining an amino acid modified alkylphenol-formaldehyde resin intermediate;

and step 3: heating the amino acid modified alkylphenol-formaldehyde resin intermediate to 100-120 ℃, distilling out most of water in the system, heating to 150-160 ℃, and steaming out residual water and unreacted monomers in a vacuum state to obtain the amino acid modified alkylphenol-formaldehyde resin.

Preferably, the catalyst is organic acid or inorganic acid, and the amount of the catalyst is 0.2-1.0% of the mass of the alkylphenol.

Preferably, the catalyst is p-toluenesulfonic acid, hydrochloric acid or sulfuric acid; the alkylphenol is one or more of p-tert-octylphenol and p-tert-butylphenol; wherein, the structural formula of the p-tert-octylphenol is as follows:

the structural formula of the p-tert-butylphenol is as follows:

preferably, the concentration of the formaldehyde aqueous solution in the step 1 is 30-40 wt%; the solid formaldehyde in the step 2 is paraformaldehyde or trioxymethylene; in the step 1, the dosage of the formaldehyde aqueous solution is 60-80% of the total mole number of formaldehyde.

Preferably, the molar ratio of the added amount of alkylphenol to formaldehyde is 1.0: 0.7-1.0:1.2, the mass ratio of the addition amount of the alkylphenol to the amino acid is 1.0:0.05-0.10,

preferably, the mole ratio of the added quantity of the alkylphenol and the formaldehyde is 1.0: 0.9-1.0: 0.95; the mass ratio of the addition amount of the alkylphenol to the amino acid is 1: 0.07-0.10.

In the preparation method, the modified alkylphenol-formaldehyde resin intermediate obtained in the step 2 is in a liquid state and is light yellow in appearance. The modified alkylphenol-formaldehyde resin obtained in the step 3 is granular or flaky solid, and the appearance is yellow to brown. The molecular weight of the product is between 1500-2000 by controlling the phenolic ratio.

The invention has the beneficial effects that:

(1) amino and carboxyl in the amino acid are all groups capable of generating strong hydrogen bond action, the reaction performance is excellent, the R group can effectively improve the intermiscibility of resin and rubber, in addition, the amino acid is a green and environment-friendly raw material, and the preparation method can adopt a protein hydrolysis method: waste materials such as feathers, human hair, and pig blood are hydrolyzed into amino acids, but most of the amino acids are "DL mixed amino acids (D-form and L-form amino acids are isomers and have high separation difficulty)" which are expensive to separate.

The crude amino acid mixture is used as a green and environment-friendly industrial raw material, DL mixed amino acid is utilized in the invention, and the DL mixed amino acid is used as a modifier to modify alkylphenol-formaldehyde resin, so that the complex separation process of the DL mixed amino acid is avoided, waste is turned into wealth, and the initial viscosity and the lasting viscosity of the resin can be greatly improved.

(2) According to the invention, alkylphenol and formaldehyde are used as raw materials, firstly, the reaction is carried out primarily under the action of an acidic catalyst to form resin intermediate alkylphenol-formaldehyde resin, then, amino acid or a mixture of a plurality of amino acids is added as a modifier for modification, and finally, solid formaldehyde is added for continuous reaction to generate the amino acid modified alkylphenol-formaldehyde resin. The preparation method has the process characteristics of simple process, high atom utilization rate and the like, and the modified alkylphenol-formaldehyde resin has extremely strong tackifying performance, and the tackifying durability and the hot and humid adhesive performance are excellent. Compared with the prior art, the invention also has the following advantages:

1. when the raw materials are used, the conditions of using solid formaldehyde are provided, so that part of formaldehyde aqueous solution is replaced, and the amount of wastewater is greatly reduced;

2. the amino acid modified alkylphenol-formaldehyde resin is selected, so that the branching degree of the product can be greatly improved, and the tackifying performance of the resin is improved;

3. the amino acid not only contains amino, carboxyl and long paraffin functional groups, but also can effectively improve the intermiscibility of the resin and the rubber material and reduce the mobility, thereby improving the lasting viscosity of the film.

4. The preparation method of the resin does not need a solvent, is simple to operate and is environment-friendly.

Detailed Description

The present invention is further illustrated by the following specific examples. In the following examples, the alkylphenol, the catalyst and the amine ionic liquid used were all commercially available.