WO2015106668A1 - Matières premières et procédé de préparation pour un adhésif de résine destiné à être utilisé dans un extrudat intégré de bambou d'agrégation - Google Patents

Matières premières et procédé de préparation pour un adhésif de résine destiné à être utilisé dans un extrudat intégré de bambou d'agrégation Download PDF

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Publication number
WO2015106668A1
WO2015106668A1 PCT/CN2015/070560 CN2015070560W WO2015106668A1 WO 2015106668 A1 WO2015106668 A1 WO 2015106668A1 CN 2015070560 W CN2015070560 W CN 2015070560W WO 2015106668 A1 WO2015106668 A1 WO 2015106668A1
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Prior art keywords
parts
bamboo
temperature
water
hydroxide
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PCT/CN2015/070560
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English (en)
Chinese (zh)
Inventor
项林
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深圳市康尔竹木业有限公司
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Publication of WO2015106668A1 publication Critical patent/WO2015106668A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/08—Ureas; Thioureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/12—Chemically modified polycondensates

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • a raw material formula of a modified phenolic resin glue and a preparation method thereof 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.
  • the patent "modified phenolic resin for bamboo structural materials and its preparation method” 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.
  • 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.
  • the patented solution still has no or good effect, and does not contribute much to the utilization value of the cluster bamboo.
  • 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.
  • 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:
  • Longzhu raw bamboo contains a high amount of protein and starch, about 5 to 10% more than bamboo;
  • the alkali content of bamboo fiber of Longzhu bamboo is about 5 ⁇ 15% lower than that of bamboo;
  • 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;
  • the fiber density of the bamboo shoots of Longzhu is low, about 25-40% lower than that of bamboo;
  • the hardness of bamboo is about twice the hardness of dragon bamboo
  • the amount of longan containing plum acid is about 5 to 10% higher than that of bamboo;
  • 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.
  • 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.
  • 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:
  • Liquid base or tablet base 8-14 Liquid base or tablet base 8-14.
  • 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:
  • 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;
  • 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;
  • 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.
  • 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.
  • sodium reacts at high temperature, it can quickly remove excess water from the integrated bamboo.
  • 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.
  • 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.
  • Liquid base or tablet base 8-14 Liquid base or tablet base 8-14.
  • 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.
  • a preparation method of a resin glue for a bundled bamboo integrated profile comprising the following steps:
  • 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;
  • 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;
  • 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.
  • a preparation method of a resin glue for a bundled bamboo integrated profile comprising the following steps:
  • 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;
  • 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.
  • a preparation method of a resin glue for a bundled bamboo integrated profile comprising the following steps:
  • 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;
  • the above method of adjusting the pH is to add an appropriate amount of water, a liquid base or a tablet base.
  • Example 1 differs from Example 1 only in that ammonium hydroxide is used as the liquid base instead of the sodium hydroxide in Example 1.
  • Example 1 differs from Example 1 only in that cesium hydroxide is used as the liquid base instead of the sodium hydroxide in Example 1.
  • This embodiment differs from Example 1 only in that a sheet base is used instead of a liquid base.
  • Example 2 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)

Abstract

L'invention concerne des matières premières et un procédé de préparation pour un adhésif de résine destiné à être utilisé dans un extrudat intégré de bambou d'agrégation. Les matières premières comprennent : du formaldéhyde, un phénol, du sulfate de sodium anhydre, de l'urée, de l'acide oléique, de la poudre de colophane et de l'eau ; elles comprennent également du propylène glycol et une solution d'hydroxyde de sodium ou des paillettes d'hydroxyde de sodium. Le procédé de préparation emploie lesdites matières premières. L'adhésif de résine de la présente invention est destiné à être utilisé dans un extrudat intégré de bambou d'agrégation. La résistance d'un extrudat de bambou collé satisfait pleinement les exigences de solidité pour un extrudat structuré. L'extrudat intégré de bambou d'agrégation ainsi fabriqué n'est pas enclin à une fissuration et à une déformation, présente une résistance élevée aux intempéries, un faible taux de détachement à l'imprégnation, est étroitement collé et ainsi n'est pas enclin à l'absorption d'humidité et présente un faible coefficient de dilatation, ce qui le rend peu enclin à une croissance de moisissures.
PCT/CN2015/070560 2014-01-17 2015-01-12 Matières premières et procédé de préparation pour un adhésif de résine destiné à être utilisé dans un extrudat intégré de bambou d'agrégation WO2015106668A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410024048.6A CN103739801B (zh) 2014-01-17 2014-01-17 丛生竹集成型材用树脂胶的原料及制备方法
CN201410024048.6 2014-01-17

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103739801B (zh) * 2014-01-17 2015-06-17 深圳市康尔竹木业有限公司 丛生竹集成型材用树脂胶的原料及制备方法
CN104493941B (zh) * 2014-12-12 2016-05-04 项林 一种用于竹木集成型材的酚醛树脂胶制造方法
CN113322035A (zh) * 2021-05-31 2021-08-31 江西亚太化工有限公司 一种环保型改性树脂及其在竹材成型上的应用

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US4663418A (en) * 1985-02-08 1987-05-05 Rutgerswerke Aktiengesellschaft Novel calcium hydroxide catalyzed phenolic resin binder and method
EP0897400B1 (fr) * 1997-02-27 2004-12-29 Borden Chemical, Inc. Composites ligneux lamines
CN102432784A (zh) * 2011-09-02 2012-05-02 新平美坚新型竹材有限公司 一种丛生竹集成型材酚醛树脂胶的原料配方及其制备方法
CN102731740A (zh) * 2012-06-28 2012-10-17 四川国能伟业科技有限公司 用多聚甲醛生产可发性酚醛树脂的方法
CN103739801A (zh) * 2014-01-17 2014-04-23 深圳市康尔竹木业有限公司 丛生竹集成型材用树脂胶的原料及制备方法

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CN100540580C (zh) * 2007-09-29 2009-09-16 福建农林大学 一种改性酚醛树脂胶的原料配方及其制备方法
CN101497777A (zh) * 2008-12-29 2009-08-05 山东万得福实业集团有限公司 一种抗水性大豆基木材胶粘剂的制备方法
CN101864053B (zh) * 2010-06-08 2012-04-18 中国林业科学研究院木材工业研究所 竹结构材用改性酚醛树脂及其制备方法
CN103242500B (zh) * 2013-05-24 2015-06-17 山东圣泉新材料股份有限公司 一种苯酚改性脲醛树脂的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4663418A (en) * 1985-02-08 1987-05-05 Rutgerswerke Aktiengesellschaft Novel calcium hydroxide catalyzed phenolic resin binder and method
EP0897400B1 (fr) * 1997-02-27 2004-12-29 Borden Chemical, Inc. Composites ligneux lamines
CN102432784A (zh) * 2011-09-02 2012-05-02 新平美坚新型竹材有限公司 一种丛生竹集成型材酚醛树脂胶的原料配方及其制备方法
CN102731740A (zh) * 2012-06-28 2012-10-17 四川国能伟业科技有限公司 用多聚甲醛生产可发性酚醛树脂的方法
CN103739801A (zh) * 2014-01-17 2014-04-23 深圳市康尔竹木业有限公司 丛生竹集成型材用树脂胶的原料及制备方法

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