阅读说明：本技术 一种竹材胶合专用酚醛树脂胶黏剂及其制备方法 (Special phenolic resin adhesive for bamboo gluing and preparation method thereof ) 是由 陈浩 沈哲红 于 2020-12-07 设计创作，主要内容包括：一种竹材胶合专用酚醛树脂胶黏剂,由如下质量份的原料制成：37wt％甲醛溶液140～180份；苯酚90～120份；40wt％氢氧化钠水溶液20～50份；正硅酸乙酯10～20份；水50～100份；乙烯基三乙氧基硅烷1～2份；甲基丙烯酸5～10份；丙烯酸正丁酯10～20份；甲基丙烯酸正丁酯10～20份；苯乙烯10～20份；羟丙基烯丙基磺酸钠5～10份；过硫酸铵0.05～0.5份；本发明酚醛树脂胶黏剂在竹青竹黄等竹材表面具有良好的润湿性和渗透性,提高带青带黄的竹材胶合强度。(The phenolic resin adhesive special for bamboo gluing is prepared from the following raw materials in parts by mass: 140-180 parts of 37 wt% formaldehyde solution; 90-120 parts of phenol; 20-50 parts of 40 wt% sodium hydroxide aqueous solution; 10-20 parts of ethyl orthosilicate; 50-100 parts of water; 1-2 parts of vinyl triethoxysilane; 5-10 parts of methacrylic acid; 10-20 parts of n-butyl acrylate; 10-20 parts of n-butyl methacrylate; 10-20 parts of styrene; 5-10 parts of sodium hydroxypropyl allylsulfonate; 0.05-0.5 part of ammonium persulfate; the phenolic resin adhesive has good wettability and permeability on the surfaces of bamboo materials such as bamboo green, bamboo yellow and the like, and improves the bonding strength of the bamboo materials with green and yellow.)

1. The phenolic resin adhesive special for bamboo gluing is characterized by being prepared from the following raw materials in parts by mass:

140-180 parts of 37 wt% formaldehyde solution; 90-120 parts of phenol; 20-50 parts of 40 wt% sodium hydroxide aqueous solution; 10-20 parts of ethyl orthosilicate; 50-100 parts of water; 1-2 parts of vinyl triethoxysilane; 5-10 parts of methacrylic acid; 10-20 parts of n-butyl acrylate; 10-20 parts of n-butyl methacrylate; 10-20 parts of styrene; 5-10 parts of sodium hydroxypropyl allylsulfonate; 0.05-0.5 part of ammonium persulfate.

2. The method for synthesizing the special phenolic resin adhesive for bamboo gluing according to claim 1, wherein the method comprises the following steps:

according to the formula, phenol, 40 wt% of sodium hydroxide aqueous solution and water are mixed, the mixture is heated to 40-55 ℃ under stirring, 60% of 37 wt% of formaldehyde aqueous solution is added, the mixture is heated to 90-95 ℃, the mixture is subjected to heat preservation reaction for 20-30 min, then the temperature is reduced to 40-55 ℃, the rest 37 wt% of formaldehyde aqueous solution is added, the mixture is heated to 90-95 ℃, the mixture is subjected to heat preservation reaction for 20-30 min, then the mixture is cooled to 40-50 ℃, ethyl orthosilicate and vinyl triethoxysilane are added for reaction for 60min, then the mixture is heated to 80-90 ℃, ammonium persulfate and sodium hydroxypropyl allylsulfonate are added, the reaction is carried out for 30min, then the mixture of methacrylic acid, n-butyl acrylate, n-butyl methacrylate and styrene is dropwise added through an injection pump, the reaction is continued for 3 hours, and the.

Technical Field

The invention relates to a special phenolic resin adhesive for bamboo gluing and a preparation method thereof.

Background

Phenolic resin is a large class of thermosetting synthetic resin prepared by condensation polymerization of phenolic compounds and aldehyde compounds. The phenol-formaldehyde resin is the most typical and important phenolic resin in phenolic resins, has excellent bonding strength and water resistance, and is widely applied to bamboo processing industries, particularly products such as recombined plates, container floors, bamboo compartment floors and bamboo building templates. However, the phenolic resin adhesive contains a benzene ring structure, and has high crosslinking density, so that the phenolic resin adhesive is easy to be brittle and easy to crack when used for bamboo gluing. Based on the novel in-situ modified phenolic resin adhesive, a flexible chain segment structure is introduced, the toughness of the phenolic resin is improved, and the brittleness is reduced.

Disclosure of Invention

The invention discloses a novel phenolic resin adhesive and a preparation method thereof.

The technical scheme of the invention is as follows:

the phenolic resin adhesive special for bamboo gluing is prepared from the following raw materials in parts by mass:

140-180 parts of 37 wt% formaldehyde solution; 90-120 parts of phenol; 20-50 parts of 40 wt% sodium hydroxide aqueous solution; 10-20 parts of ethyl orthosilicate; 50-100 parts of water; 1-2 parts of vinyl triethoxysilane; 5-10 parts of methacrylic acid; 10-20 parts of n-butyl acrylate; 10-20 parts of n-butyl methacrylate; 10-20 parts of styrene; 5-10 parts of sodium hydroxypropyl allylsulfonate; 0.05-0.5 part of ammonium persulfate.

The synthetic method of the special phenolic resin adhesive for bamboo gluing comprises the following steps:

according to the formula, phenol, 40 wt% of sodium hydroxide aqueous solution and water are mixed, the mixture is heated to 40-55 ℃ under stirring, 60% of 37 wt% of formaldehyde aqueous solution is added, the mixture is heated to 90-95 ℃ within 50-60 min, the mixture is subjected to heat preservation reaction for 20-30 min, then the mixture is cooled to 40-55 ℃, the remaining 37 wt% of formaldehyde aqueous solution (namely 40% of the total amount) is added, the mixture is heated to 90-95 ℃ and subjected to heat preservation reaction for 20-30 min, then the mixture is cooled to 40-50 ℃, ethyl orthosilicate and vinyl triethoxysilane are added, the mixture is subjected to reaction for 60min, then the mixture is heated to 80-90 ℃, ammonium persulfate and sodium hydroxypropyl allylsulfonate are added, the reaction is carried out for 30min, then the mixed solution of methacrylic acid, n-butyl acrylate, n-butyl methacrylate and styrene is dropwise added through an injection pump within 2 hours, the reaction is continued for 3 hours.

The invention has the beneficial effects that:

the phenolic resin adhesive prepared by the invention has good fluidity and bonding performance, and is used for directly bonding yellow bamboo materials with green tapes. The phenolic resin adhesive added with the modifier has boiling water boiling resistance of 20 minutes when the green bamboos are glued, boiling water boiling resistance of 140 minutes when the tabasheers are glued, the phenolic resin adhesive without the modifier has boiling water boiling resistance of 6 minutes when the green bamboos are glued, and boiling water boiling resistance of 60 minutes when the tabasheers are glued, so that the gluing performance of the modified phenolic resin is obviously improved.

Detailed Description

The invention is further described below by means of specific examples, without restricting its scope to these.

Example 1

(1) 100g of phenol, 20g of 40 wt% sodium hydroxide and 50g of water are added into a reaction kettle, and the temperature is uniformly raised to 55 ℃ under stirring.

(2) Slowly adding 90g of formaldehyde solution with the weight percent of 37 percent and the total weight of 60 percent, heating to 95 ℃ within 50min, and reacting for 30min under the condition of heat preservation.

(3) After the heat preservation time is finished, cooling to 55 ℃, adding 60g of the residual 37 wt% formaldehyde solution, heating to 95 ℃, and carrying out heat preservation reaction for 30 min.

(4) After the reaction is carried out under the condition of heat preservation, the temperature is reduced to about 40 ℃, 1g of tetraethoxysilane and 1g of vinyl triethoxysilane are added, and the reaction is carried out for 60 min.

(5) After the reaction is finished, the temperature is raised to 85 ℃, 0.1g of ammonium persulfate and 0.1g of sodium hydroxypropyl allylsulfonate are added, and the reaction is carried out for 30 min.

(6) 1g of methacrylic acid, 10g of n-butyl acrylate, 10g of n-butyl methacrylate and 5g of styrene were added dropwise over 2 hours by means of a syringe pump and the reaction was continued for 3 hours.

(7) After the heat preservation is finished, cooling to 35 ℃, discharging and storing.

The phenolic resin adhesive prepared by the embodiment has good fluidity and bonding performance, and is used for directly bonding yellow bamboo materials with green tapes. The boiling water resistant cooking time is 20 minutes when the bamboo green and the bamboo green are glued, the boiling water resistant cooking time is 140 minutes when the bamboo yellow and the bamboo yellow are glued,

example 2

(1) 100g of phenol, 20g of 40 wt% sodium hydroxide and 50g of water are added into a reaction kettle, and the temperature is uniformly raised to 55 ℃ under stirring.

(2) Slowly adding 90g of formaldehyde solution with the weight percent of 37 percent and the total weight of 60 percent, heating to 95 ℃ within 50min, and reacting for 30min under the condition of heat preservation.

(3) After the heat preservation time is finished, cooling to 55 ℃, adding 60g of the residual 37 wt% formaldehyde solution, heating to 95 ℃, and carrying out heat preservation reaction for 30 min.

(4) After the reaction is carried out under the condition of heat preservation, the temperature is reduced to about 40 ℃, 2g of tetraethoxysilane and 2g of vinyl triethoxysilane are added, and the reaction is carried out for 60 min.

(5) After the reaction is finished, the temperature is raised to 85 ℃, 0.1g of ammonium persulfate and 0.1g of hydroxypropyl sodium allylsulfonate are added, and the reaction is carried out for 30 min.

(6) 1g of methacrylic acid, 10g of n-butyl acrylate, 10g of n-butyl methacrylate and 5g of styrene were added dropwise over 2 hours by means of a syringe pump and the reaction was continued for 3 hours.

(7) After the heat preservation is finished, cooling to 35 ℃, discharging and storing.

The phenolic resin adhesive prepared by the embodiment has good fluidity and bonding performance, and is used for directly bonding yellow bamboo materials with green tapes. When the bamboo green and the bamboo green are glued, the boiling water resistant cooking time is 25 minutes, when the bamboo yellow and the bamboo yellow are glued, the boiling water resistant cooking time is 150 minutes,

example 3

(1) 100g of phenol, 20g of 40 wt% sodium hydroxide and 50g of water are added into a reaction kettle, and the temperature is uniformly raised to 55 ℃ under stirring.

(2) Slowly adding 90g of formaldehyde solution with the weight percent of 37 percent and the total weight of 60 percent, heating to 95 ℃ within 50min, and reacting for 30min under the condition of heat preservation.

(3) After the heat preservation time is finished, cooling to 55 ℃, adding 60g of the residual 37 wt% formaldehyde solution, heating to 95 ℃, and carrying out heat preservation reaction for 30 min.

(4) After the reaction is carried out under the condition of heat preservation, the temperature is reduced to about 40 ℃, 2g of tetraethoxysilane and 2g of vinyl triethoxysilane are added, and the reaction is carried out for 60 min.

(5) After the reaction is finished, the temperature is raised to 85 ℃, 0.2g of ammonium persulfate and 0.1g of hydroxypropyl sodium allylsulfonate are added, and the reaction is carried out for 30 min.

(6) 1g of methacrylic acid, 15g of n-butyl acrylate, 15g of n-butyl methacrylate and 10g of styrene are added dropwise over 2 hours by means of a syringe pump and the reaction is continued for 3 hours.

(7) After the heat preservation is finished, cooling to 35 ℃, discharging and storing.

The phenolic resin adhesive prepared by the embodiment has good fluidity and bonding performance, and is used for directly bonding yellow bamboo materials with green tapes. The boiling water resistant steaming time is 28 minutes when the bamboo green and the bamboo green are glued, the boiling water resistant steaming time is 153 minutes when the bamboo yellow and the bamboo yellow are glued,

comparative example:

(1) 100g of phenol, 20g of 40 wt% sodium hydroxide and 50g of water are added into a reaction kettle, and the temperature is uniformly raised to 55 ℃ under stirring.

(2) Slowly adding 90g of formaldehyde solution with the weight percent of 37 percent and the total weight of 60 percent, heating to 95 ℃ within 50min, and reacting for 30min under the condition of heat preservation.

(3) After the heat preservation time is finished, cooling to 55 ℃, adding 60g of the residual 37 wt% formaldehyde solution, heating to 95 ℃, and carrying out heat preservation reaction for 60 min.

(4) After the heat preservation is finished, cooling to 35 ℃, discharging and storing.

When the phenolic resin adhesive is used for gluing the bamboo green and the bamboo green, the boiling and boiling resistant time is 6 minutes, and when the bamboo yellow is glued with the bamboo yellow, the boiling and boiling resistant time is 60 minutes, so that the gluing performance of the modified phenolic resin is obviously improved in comparison with a proportion.