WO2015106668A1

WO2015106668A1 - Raw materials and preparation method for resin adhesive for use in clumping bamboo integrated extrudate

Info

Publication number: WO2015106668A1
Application number: PCT/CN2015/070560
Authority: WO
Inventors: 项林
Original assignee: 深圳市康尔竹木业有限公司
Priority date: 2014-01-17
Filing date: 2015-01-12
Publication date: 2015-07-23
Also published as: CN103739801A; CN103739801B

Abstract

Disclosed are raw materials and a preparation method for a resin adhesive for use in a clumping bamboo integrated extrudate. The raw materials comprise: formaldehyde, a phenol, anhydrous sodium sulfate, urea, oleic acid, rosin powder, and water, also comprise propylene glycol and caustic soda solution or caustic soda flakes. The preparation method employs said raw materials. The resin adhesive of the present invention is for use in a clumping bamboo integrated extrudate. The strength of a glued bamboo extrudate fully meets a strength requirement for a structured extrudate. The clumping bamboo integrated extrudate so manufactured is not prone to cracking and deformation, high in weather resistance, low in impregnation peel rate, tightly glued, thus not prone to moisture absorption, and small in expansion coefficient, thus not prone to mold growth.

Description

Raw material and preparation method of resin adhesive for cluster bamboo integrated profile

Technical field

The invention relates to a bamboo integrated profile, in particular to a raw material and a preparation method of a resin adhesive for a bundled bamboo integrated profile.

Background technique

At present, the wood-based panels and integrated profiles of bamboo and wood are all made of phenolic resin. The phenolic resin has many properties such as heat resistance, electrical insulation, water resistance, weather resistance, high mechanical strength and flame retardancy. In adhesives, paint materials and anti-wear materials, researchers continue to explore phenolic resins to improve the bonding strength of phenolic resins, heat resistance and wear resistance of resins. However, the existing bamboo can only use the loose bamboo as a raw material, and it is impossible to use the cluster bamboo as a processing raw material.

Congsheng bamboo (such as dragon bamboo) has a high rod diameter, a large diameter, and a material yield per unit area that is 4 to 6 times higher than that of China's main economic bamboo (such as bamboo). The fiber of the cluster bamboo is coarse and the fiber accounts for all of the stems. More than 50% of the tissue, the bamboo bamboo performance is not good for loose bamboo, its low density, low strength and other factors are not good to use the root cause. Because of the thick bamboo fiber, high moisture, sugar, starch, protein, plum acid and other molecules than the bamboo content is much higher, it is easy to be worms, mildew and rot, so the practical performance is very poor.

The patent "a raw material formula of a modified phenolic resin glue and a preparation method thereof" (patent application number: 200710009600) discloses a raw material formula of a modified phenolic resin glue and a preparation method thereof, and the raw materials used are: phenol, carbon Amide, formaldehyde, liquid alkali and water. The preparation process is divided into two steps. First, the carbonic acid amide and a part of formaldehyde are made into a solid addition of carbonic acid amide and formaldehyde, and then added and reacted in the synthesis process of the phenolic resin. The phenolic resin glue prepared by the method is suitable for the use of wood and scattered bamboo wood-based panels. For example, the patent "modified phenolic resin for bamboo structural materials and its preparation method" (patent application number: 201010200167) discloses a bamboo structural material glue prepared by combining the structural characteristics of bamboo, and the preparation raw material is a phenolic storage liquid. 35 to 85%; 0 to 40% aqueous formaldehyde solution; 7 to 20% alkaline aqueous solution; and resorcinol 0.5 to 5%. The preparation method comprises the following steps: adding a phenolic storage solution to the reaction vessel, adding the aqueous formaldehyde solution for the first time, adding an alkaline aqueous solution, raising the temperature to 30 to 70 ° C, reacting for 30 to 90 minutes, adding an aqueous formaldehyde solution, and heating to 70 to 98 ° C. The reaction was carried out for 20 to 90 minutes, and then an alkaline aqueous solution was added to react with resorcinol until the viscosity of the test solution was 15 to 700 mPa.s. The modified phenolic resin glue prepared by the method has certain modification to the bonding performance of the scattered bamboo material. Good, but the improvement of the bonding performance of the bamboo is very small. The patent "a raw material formula of a plexiform bamboo integrated profile phenolic resin glue and a preparation method thereof" (Patent No.: 201110257647.9) discloses the use of formaldehyde, phenol, anhydrous sodium sulfate, urea, oleic acid, rosin powder, water, ethane diacetic acid. And the liquid alkali is used as a raw material to prepare the resin glue for the integrated bamboo integrated profile. However, the patented solution still has no or good effect, and does not contribute much to the utilization value of the cluster bamboo.

Summary of the invention

The technical problem to be solved by the present invention is to provide a resin rubber raw material for a bundled bamboo integrated profile and a preparation method of a resin for a bundled bamboo integrated profile to meet the rubber demand of the integrated bamboo integrated profile.

According to the study by the present inventors, the reason why the bamboo shoots are difficult to be used for preparing the integrated sheet mainly lies in the physiological structure of the cluster bamboo and the specificity of the molecular structure, and the inventors have conducted in-depth research on the factors affecting the utilization of the cluster bamboo sheets, and Based on the research, the solution of the invention is obtained. as follows:

The following are the physiological data and molecular tissue content of the cluster bamboo (taking Longzhu as an example) and the scattered bamboo (taking Bamboo as an example):

1. Long bamboo raw bamboo has a high moisture content, which is about 15-20% higher than that of bamboo.

2, Longzhu raw bamboo sugar content is high, about 5 to 10% more than bamboo;

3, Longzhu raw bamboo contains a high amount of protein and starch, about 5 to 10% more than bamboo;

4, Longzhuyuan bamboo and bamboo fiber is coarse, about 45 to 50% more than bamboo;

5. The alkali content of bamboo fiber of Longzhu bamboo is about 5~15% lower than that of bamboo;

6. The dragon bamboo bamboo section is a cotton mesh screen structure, and the thickness of the bamboo joint is about 100-200% higher than that of the bamboo;

7. The fiber density of the bamboo shoots of Longzhu is low, about 25-40% lower than that of bamboo;

8, the hardness of bamboo is about twice the hardness of dragon bamboo;

9, the amount of longan containing plum acid is about 5 to 10% higher than that of bamboo;

10. Longzhu and bamboo glue are bonded into performance test; the same polyvinyl acetate (PVAc) adhesive is used to glue the dragon bamboo and bamboo together with the same glue pressure of equal volume of bamboo. Bamboo bears only 78% of fiber breakage at pressures above 10 Newtons per square millimeter, whereas bundled bamboos have a fiber breakage of only 7 Newtons per square millimeter.

In summary, the bamboos and loose bamboos have different long-climate geography conditions, and their fiber structure and composition are different. The bamboo fibers are thicker, and the contents of sugar, starch and plum acid are higher than those of bamboo. The water content of bamboo bamboo and bamboo fiber is very different, the water content of bamboo is very low, and the water content of bamboo is very high. When drying, the bamboo fiber shrinks little, while the bamboo part shrinks greatly. Based on the above differences, the existing resin glue is applied to the cluster bamboo. Since the phenolic resin glue is not prepared according to the characteristics of the cluster bamboo, the adhesive strength requirement of the bundled bamboo integrated profile cannot be achieved, and it is easy to deform, crack, expand, mold and not reach. To the requirements of normal use. This is the main reason why the bamboo has not been exploited for many years.

Based on the above analysis, the present invention solves the problem that cluster bamboo is difficult to use for preparing integrated profiles by the following technical solutions:

A raw material for a resin adhesive for a bamboo integrated profile, comprising: formaldehyde, phenol, anhydrous sodium sulfate, urea, oleic acid, rosin powder and water, and also includes propylene glycol, and a liquid base or a tablet base, each component by mass percentage Count as:

Formaldehyde 70-110 parts

Phenol 40-60 parts

Anhydrous sodium sulfate 10-35 parts

Urea 10-25 parts

Oleic acid 3-8 parts

1-3 parts of rosin powder

35-60 parts of water

Propylene glycol 1-5 parts

Liquid base or tablet base 8-14.

Preferably, the liquid base is any one or a mixture of two or more of ammonium hydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide having a water content of less than 1% by mass; Any one or a mixture of two or more of ammonium, sodium hydroxide, potassium hydroxide, and barium hydroxide.

A preparation method of a resin glue for a bundled bamboo integrated profile, comprising the following steps:

S1, take 50-70 parts of formaldehyde, 40-60 parts of phenol, 1-5 parts of propylene glycol, 5-8 parts of liquid alkali or caustic soda, and 15-25 parts of water, add to the reaction kettle and stir evenly, then add appropriate amount of water and liquid alkali. Or the pH of the base adjustment mixture is 7-8, then the temperature is raised to 65-85 ° C, and then the reaction is kept for 70-100 min, and the temperature is also controlled during the heat preservation. Made in the range of 65 ~ 85 ° C;

S2, after 70 to 100 minutes of heat preservation, the pH of the reaction product is adjusted to 7-8 by adding an appropriate amount of water, liquid alkali or caustic soda, and then the temperature is lowered to 65 to 70 ° C;

S3, after the temperature is lowered to 65-70 ° C, 20-40 parts of formaldehyde is added to the reaction product, 10-35 parts of anhydrous sodium sulfate, stirred uniformly, and then heated to 80-85 ° C, and the heat preservation reaction is 80-100 min;

S4, after the reaction is completed, the pH of the reaction product is adjusted to 7 to 9 by adding an appropriate amount of water, liquid alkali or caustic soda, and then the temperature is lowered to 55 to 65 ° C, and then 10 to 25 parts of urea is added to the reaction product, and the mixture is uniformly stirred. The temperature is raised to 55-70 ° C, and then added -8 parts of oleic acid, 3-6 parts of liquid alkali, 20 ~ 35 parts of water, stirred evenly, heated to 85 ~ 99 ° C and kept 60 ~ 100min;

S5, after 60 to 100 minutes of heat preservation, the temperature is lowered to 45 to 50 ° C, and then 1-3 parts of rosin powder is added and stirred for 30 minutes or more. After the completion of the stirring, the temperature is lowered to 45 ° C or less to obtain a resin glue for the integrated bamboo integrated profile.

The liquid base is any one or a mixture of two or more kinds of ammonium hydroxide, sodium hydroxide, potassium hydroxide or barium hydroxide having a water content of less than 1% by mass; the plate base is ammonium hydroxide and hydrogen Any one or a mixture of two or more of sodium oxide, potassium hydroxide, and barium hydroxide.

Unless otherwise stated, the parts of the patent refer to parts by mass.

Compared with the prior art, the rubber compound of the invention combines the characteristics of the bamboo structure, and an anhydrous sodium sulfate, oleic acid, propylene glycol, rosin powder and the like are added to the resin glue, and anhydrous sulphuric acid is added to the modified phenolic resin glue. When sodium reacts at high temperature, it can quickly remove excess water from the integrated bamboo. During the high-temperature molding process, oleic acid oxidation can increase the hardening degree of the profile, and the addition of rosin powder increases the viscose strength of the phenolic resin glue. The fiber bonding ability is greatly enhanced, and the integrated bamboo integrated profiles are not easy to crack and deform, have high weather resistance, low immersion and peeling rate, tight adhesion and water absorption, and small Peng coefficient without being mildewed. The propylene glycol combined with anhydrous sodium sulphate and other components can promote the rapid dispersion of the liquid glue absorbed by the bamboo sheet under the high temperature reaction and solidification, so that the liquid glue component is balanced to penetrate into each part of each bamboo piece, thereby achieving the integrated The inner and outer gluing strength of the bamboo profiles are consistent. The resin glue prepared by the method of the invention is a transparent liquid with stable performance, strong bonding property, good weather resistance, low immersion peeling rate and fast curing speed. The resin glue is used in the integrated bamboo integrated profile, and the strength of the glued bamboo profile is It can fully meet the strength requirements of structural materials, thus actively promoting the application of bamboo materials, broadening the utilization range of bamboo materials, so that the bamboo materials that have not been processed and utilized can be processed and utilized, turning waste into treasure. The method of the invention has simple process, and only needs the quantitative determination of the raw materials to be accurately added in stages, and the temperature required for the control phase is fully reacted, throughout The operation is simple and safe in the preparation process, and does not require dehydration, no pollutants, and is energy-saving and environmentally friendly.

detailed description

The invention will now be further described in conjunction with the preferred embodiments.

A resin glue raw material for a bamboo integrated structural profile, comprising: wherein: the liquid alkali is any one or two of ammonium hydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide having a water content of less than 1% by mass The above mixture is a mixture of any one or a mixture of two or more of ammonium hydroxide, sodium hydroxide, potassium hydroxide, and barium hydroxide.

Formaldehyde 70-110 parts

Phenol 40-60 parts

Anhydrous sodium sulfate 10-35 parts

Urea 10-25 parts

Oleic acid 3-8 parts

1-3 parts of rosin powder

35-60 parts of water

Propylene glycol 1-5 parts

Liquid base or tablet base 8-14.

Wherein: the liquid base is any one or a mixture of two or more of ammonium hydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide having a water content of less than 1% by mass; the tablet base is ammonium hydroxide Any one or a mixture of two or more of sodium hydroxide, potassium hydroxide and barium hydroxide.

S1, take 50-70 parts of formaldehyde, 40-60 parts of phenol, 1-5 parts of propylene glycol, 5-8 parts of liquid alkali or caustic soda, and 15-25 parts of water, add to the reaction kettle and stir evenly, then add appropriate amount of water and liquid alkali. Or the pH of the base adjustment mixture is 7-8, then the temperature is raised to 65-85 ° C, and then the reaction is kept for 70-100 min, and the temperature is also controlled within the range of 65-85 ° C;

S4. After the reaction is completed, the pH of the reaction product is adjusted to 7-9 by adding an appropriate amount of water, liquid alkali or caustic soda. After cooling to 55 ~ 65 ° C, then add 10 ~ 25 parts of urea to the reaction product, stir evenly, the temperature is raised to 55-70 ° C, then add -8 parts of oleic acid, 3-6 parts of liquid alkali, 20 to 35 parts of water, stir evenly, then raise the temperature to 85 ~ 99 ° C and keep warm for 60 ~ 100min;

Example 1

S1, 50 parts of formaldehyde, 60 parts of phenol, 1 part of propylene glycol, 5 parts of liquid alkali (sodium hydroxide) having a water content of less than 1%, and 15 parts of water are added to the reaction vessel and stirred uniformly to adjust the pH of the mixture to 7~ 8, then warmed to 65 ° C, and then the reaction was held for 70 min, the temperature was also controlled at about 65 ° C;

S2, after the incubation for 70 min, the pH of the reaction product is adjusted to 7-8, and then the temperature is lowered to 65 ° C;

S3, after the temperature is lowered to 65 ° C, 20 parts of formaldehyde is added to the reaction product, 10 parts of anhydrous sodium sulfate, stirred uniformly, and then heated to 80 ° C, and the reaction is kept for 80 minutes;

S4. After the reaction is completed, the pH of the reaction product is adjusted to 7 to 9 by adding an appropriate amount of water, liquid alkali or caustic soda, and then the temperature is lowered to 55 ° C, and then 10 parts of urea is added to the reaction product, and the temperature is raised to 55 after stirring uniformly. °C, then add 3 parts of oleic acid, 3 parts of liquid alkali, 20 parts of water, stir evenly, then warm to 85 ° C and keep warm for 60 min;

S5, after 60min heat preservation, the temperature is lowered to 45~50°C, and then 1% rosin powder is added and stirred for more than 30min. After the completion of the stirring, the temperature is lowered to below 45°C to obtain the resin glue for the integrated bamboo integrated profile.

The above method of adjusting the pH is to add an appropriate amount of water, a liquid base or a tablet base.

Example 2

S1, 70 parts of formaldehyde, 60 parts of phenol, 5 parts of propylene glycol, 8 parts of caustic soda (potassium hydroxide), 25 parts of water are added to the reaction vessel and stirred uniformly. The pH of the mixture is adjusted by adding an appropriate amount of water, liquid alkali or caustic soda. 8 , then the temperature is raised to 85 ° C, and then the reaction is kept for 100 min, the temperature is also controlled at about 85 ° C;

S2, after the incubation for 100 min, the pH of the reaction product is adjusted to 7-8, and then the temperature is lowered to 70 ° C;

S3, after the temperature is lowered to 70 ° C, 40 parts of formaldehyde and 135 parts of anhydrous sodium sulfate are added to the reaction product. After stirring evenly, the temperature was raised to 85 ° C, and the reaction was kept for 100 min;

After the reaction is completed, the pH of the reaction product is adjusted to 7-9, and then the temperature is lowered to 65 ° C, and then 25 parts of urea is added to the reaction product. After stirring uniformly, the temperature is raised to 70 ° C, and 8 parts of oleic acid is added thereto. 6 parts of liquid alkali, 35 parts of water, stir evenly, then heat up to 99 ° C and keep warm for 100 min;

S5, after cooling for 100min, the temperature is lowered to 50 °C, and then 3 parts of rosin powder is added and stirred for more than 30 minutes. After the completion of the stirring, the temperature is lowered to below 45 °C to obtain the resin glue for the integrated bamboo integrated profile.

Example 3

This example differs from Example 1 only in that ammonium hydroxide is used as the liquid base instead of the sodium hydroxide in Example 1.

Example 4

This example differs from Example 1 only in that cesium hydroxide is used as the liquid base instead of the sodium hydroxide in Example 1.

Example 5

This embodiment differs from Example 1 only in that a sheet base is used instead of a liquid base.

Example 6

This example differs from Example 2 only in that potassium hydroxide having a water content of less than 1% by mass is used as a liquid base instead of the sheet base in Example 2.

It has been tested that the resin glue prepared in the above embodiment is used in the integrated bamboo integrated profile, and the strength of the glued bamboo profile can fully meet the strength requirement of the structural material, and the assembled bamboo integrated profile is not easy to crack deformation, high weather resistance, and immersion peeling. The rate is low, the adhesion is tight, the water absorption is not easy, the expansion coefficient is small, and it is not easy to be mildewed.

The above is a further detailed description of the present invention in connection with the specific preferred embodiments, and the specific embodiments of the present invention are not limited to the description. It will be apparent to those skilled in the art that <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

Claims

The invention relates to a raw material for a resin adhesive for a bamboo integrated profile, which comprises: formaldehyde, phenol, anhydrous sodium sulfate, urea, oleic acid, rosin powder and water, further comprises propylene glycol, and liquid alkali or caustic soda, each group The quality by weight includes:

Formaldehyde 70-110 parts

Phenol 40-60 parts

Anhydrous sodium sulfate 10-35 parts

Urea 10-25 parts

Oleic acid 3-8 parts

Rosin powder 1-3 parts

Water 35-60 servings

Propylene glycol 1-5 parts

Liquid base or tablet base 8-14 parts.
The raw material for a resin adhesive for a bamboo-integrated profile according to claim 1, wherein the liquid alkali is ammonium hydroxide, sodium hydroxide, potassium hydroxide or barium hydroxide having a water content of less than 1% by mass. Any one or a mixture of two or more; the tablet base is any one or a mixture of two or more of ammonium hydroxide, sodium hydroxide, potassium hydroxide, and barium hydroxide.
A method for preparing a resin adhesive for a bundled bamboo integrated profile, comprising the steps of:

S1, take 50-70 parts of formaldehyde, 40-60 parts of phenol, 1-5 parts of propylene glycol, 5-8 parts of liquid alkali or caustic soda, and 15-25 parts of water, add to the reaction kettle and stir evenly, then add appropriate amount of water and liquid alkali. Or the pH of the base adjustment mixture is 7-8, then the temperature is raised to 65-85 ° C, and then the reaction is kept for 70-100 min, and the temperature is also controlled within the range of 65-85 ° C;

S2, after 70 to 100 minutes of heat preservation, the pH of the reaction product is adjusted to 7-8 by adding an appropriate amount of water, liquid alkali or caustic soda, and then the temperature is lowered to 65 to 70 ° C;

S3, after the temperature is lowered to 65-70 ° C, 20-40 parts of formaldehyde is added to the reaction product, 10-35 parts of anhydrous sodium sulfate, stirred uniformly, and then heated to 80-85 ° C, and the heat preservation reaction is 80-100 min;

S4, after the reaction is completed, the pH of the reaction product is adjusted to 7 to 9 by adding an appropriate amount of water, liquid alkali or caustic soda, and then the temperature is lowered to 55 to 65 ° C, and then 10 to 25 parts of urea is added to the reaction product, and the mixture is uniformly stirred. Temperature Raise to 55 ~ 70 ° C, then add -8 parts of oleic acid, 3 ~ 6 parts of liquid alkali, 20 ~ 35 parts of water, stir evenly and then warm to 85 ~ 99 ° C and keep warm for 60 ~ 100min;

S5, after 60 to 100 minutes of heat preservation, the temperature is lowered to 45 to 50 ° C, and then 1-3 parts of rosin powder is added and stirred for 30 minutes or more. After the completion of the stirring, the temperature is lowered to 45 ° C or less to obtain a resin glue for the integrated bamboo integrated profile.
The preparation method according to claim 3, wherein the liquid base is any one or two of ammonium hydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide having a water content of less than 1% by mass. The above mixture; the tablet base is any one or a mixture of two or more of ammonium hydroxide, sodium hydroxide, potassium hydroxide, and barium hydroxide.