WO2013020344A1 - 水溶性改性三聚氰胺甲醛浸渍树脂及其制备方法和应用 - Google Patents

水溶性改性三聚氰胺甲醛浸渍树脂及其制备方法和应用 Download PDF

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WO2013020344A1
WO2013020344A1 PCT/CN2011/084796 CN2011084796W WO2013020344A1 WO 2013020344 A1 WO2013020344 A1 WO 2013020344A1 CN 2011084796 W CN2011084796 W CN 2011084796W WO 2013020344 A1 WO2013020344 A1 WO 2013020344A1
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soluble
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formaldehyde
resin
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South China University of Technology SCUT
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
    • C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
    • C08G12/427—Melamine
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine

Definitions

  • the invention relates to a water-soluble modified melamine formaldehyde impregnating resin which can be used in the furniture and paper industry, such as paper edge strips and decorative paper, and a preparation method thereof, and belongs to the fields of furniture manufacturing and paper making.
  • Melamine formaldehyde resin is a thermosetting resin. It has flame retardant, water resistance, heat resistance, aging resistance, arc resistance, chemical resistance, good insulation properties, gloss and mechanical strength. It is widely used in wood furniture and plastics. Coatings, paper, textile, leather, electrical, pharmaceutical and other industries. However, its shortness of brittleness, short shelf life, toxicity of organic solvents and high volatility limit its further wide application. To this end, research on its modification has become a hot topic.
  • the modification methods can be divided into physical modification and chemical modification.
  • the main purpose is to change the former oil-soluble resin into water-soluble resin, reduce the disadvantages of organic solvent toxicity and volatility, increase toughness, reduce formaldehyde content and Improve resin stability, physical modification mainly by adding some flexible polymers to increase the toughness of melamine formaldehyde resin, such as silicone, polyvinyl alcohol, polyacrylamide and polyvinyl acetate, etc., chemical modification mainly through melamine formaldehyde In the prepolymerization process of the resin, reactive molecules such as alcohols and urea are added to improve water solubility, reduce formaldehyde content, and improve resin stability.
  • the modification of the resin is often carried out by a modification means, the modification effect can only achieve a modification purpose and often improves the performance on the one hand, and loses other excellent properties, such as adding only flexibility.
  • the polymer toughening agent can not improve the stability of the resin, and often loses its excellent properties such as good surface hardness and wear resistance.
  • the object of the present invention is to overcome the shortcomings of the prior art, and to modify a physical and chemical modification method to provide a comprehensive performance with good toughness, low formaldehyde content and long-term stability. Water-soluble modified melamine formaldehyde impregnating resin and preparation method thereof.
  • the preparation method of water-soluble modified melamine formaldehyde impregnating resin adopts water-soluble methyl etherified melamine formaldehyde resin as matrix, water-soluble acrylate emulsion and water-soluble polyurethane emulsion as toughening agent and modifier respectively, and composite preparation Out, the specific steps are as follows:
  • the raw material formula is: in terms of weight percent, acrylate monomer 36-56%, 40-60% styrene, 2-3% emulsifier, 0.5-1.5% initiator; initiator, all the above monomers (acrylic acid)
  • the ester monomer and styrene) and part of the emulsifier and deionized water are mixed for pre-emulsification; then the remaining emulsifier is dissolved in deionized water at 70-80 oC, under nitrogen protection, the pre-emulsion of the above monomer is added to the above solution to react for 2-4 hours, then the temperature is lowered to 60-70 oC, and ammonia water is added for adjustment.
  • PH 8.0, to obtain a water-soluble acrylate emulsion toughening agent;
  • the raw material formula is: 25-40% by weight of toluene diisocyanate, 55-70% of polyether, 1-4% of dimethylolpropionic acid, 3-5% of ethylenediamine; toluene diisocyanate, polyether , dimethylolpropionic acid at 80 Pre-polymerization reaction at oC for 3-4 hours, cooling to 10-30 oC, adding deionized water to emulsify, adding ethylenediamine chain extension reaction for 1-1.5 hours to obtain a water-soluble polyurethane emulsion modifier;
  • the water-soluble methyl etherified melamine formaldehyde resin, the acrylate emulsion toughening agent and the polyurethane emulsion modifier prepared above are respectively carried out in terms of weight percentage: 50 to 90%, 5 to 30%, and 0 to 20%. Mixing, that is, producing a water-soluble modified melamine formaldehyde resin.
  • the water-soluble methyl etherified melamine formaldehyde resin, the acrylate emulsion toughening agent and the polyurethane emulsion modifier are 50 to 90%, 5 to 20% and 0 to 10%, respectively, by weight.
  • the acrylate monomer is methyl methacrylate 10-37%, butyl acrylate 54-85% And a mixture of 0-17% acrylic acid.
  • the emulsifier is a mixture of one or both of sodium lauryl sulfate and nonylphenol ethoxylate.
  • the initiator is a mixture of one or both of potassium persulfate and ammonium persulfate.
  • the partial emulsifier added in the pre-emulsification in the step (2) is 10 to 90% of the total amount of the emulsifier.
  • a pull-up powder (sodium butyl naphthalenesulfonate) of 0.05-1% by weight of the total amount of the raw materials is further added.
  • reaction of step (1) is finally added with 0.05-5% urea or emulsified rosin in total weight of the raw materials.
  • the water-soluble modified melamine formaldehyde impregnating resin prepared by the above method is used for impregnation of paper edge strips and decorative paper in furniture and papermaking.
  • the invention has the following advantages:
  • the water-soluble modified melamine formaldehyde impregnating resin of the invention has good flexibility, and is particularly suitable for impregnation of paper edge strips and decorative papers in furniture and papermaking, and the paper edge strips prepared can be rotated at any angle of 0-180o.
  • the surface coating hardness is up to H grade (pencil hardness) and can be stored for 6 months at room temperature.
  • the water-soluble melamine formaldehyde impregnating resin of the present invention has long-term stability and can be stored for 3 to 6 months.
  • the water-soluble modified melamine formaldehyde impregnating resin of the invention is an environment-friendly material, and the residual formaldehyde content is less than the national standard 1.3 Mg/kg.
  • the problem of high toxicity and high volatility and high residual formaldehyde content of the organic solvent used in the oil-soluble impregnating resin has been improved, and environmentally-friendly green production has been achieved, thereby achieving energy saving and emission reduction.
  • Figure 1 is an infrared spectrum of a water-soluble methyl etherified melamine formaldehyde resin.
  • Figure 2 is an infrared spectrum of a water-soluble acrylate emulsion toughening agent.
  • Figure 3 is an infrared spectrum of a water-soluble polyurethane modifier.
  • Step 1 Preparation of water-soluble methyl etherified melamine formaldehyde resin:
  • Step 2 Preparation of water-soluble acrylate emulsion toughening agent:
  • Step 3 Preparation of water-soluble polyurethane emulsion modifier:
  • toluene diisocyanate 180g of polyether, 6g of dimethylolpropionic acid and 9g of ethylenediamine.
  • the synthesis process is as follows: adding toluene diisocyanate, polyether and dimethylolpropionic acid to the reactor at 80 The prepolymerization reaction was carried out for 3.5 hours at oC, and the temperature was lowered to 25 ° C, emulsified by adding 100 mL of deionized water, and 9 g of ethylenediamine was added for chain extension reaction for 1 hour, and a water-soluble polyurethane emulsion modifier was prepared by discharging.
  • Step 4 180 g of the water-soluble methyl etherified melamine formaldehyde resin, 54 g of the acrylate emulsion toughening agent and 18 g of the polyurethane emulsion modifier are mixed to obtain a water-soluble modified melamine formaldehyde resin. It is used for the impregnation of edge banding paper. It has good flexibility. It is easy to rotate in the edge of furniture (0-180o), the surface coating hardness is H grade (pencil hardness), it can be stored for 6 months at room temperature, residual formaldehyde content. 1.1 Mg/kg.
  • Step 1 Preparation of water-soluble methyl etherified melamine formaldehyde resin:
  • Step 2 Preparation of water-soluble acrylate emulsion toughening agent:
  • Step 3 Preparation of water-soluble polyurethane emulsion modifier:
  • toluene diisocyanate 180g of polyether, 6g of dimethylolpropionic acid and 9g of ethylenediamine.
  • the synthesis process is as follows: adding toluene diisocyanate, polyether and dimethylolpropionic acid to the reactor at 80 Prepolymerization at oC for 3.5 hours, cooling to 25 oC, emulsification by adding 100 mL of deionized water, adding ethylenediamine chain extension reaction for 1 hour, and discharging to obtain a water-soluble polyurethane emulsion modifier.
  • Step 4 180 g of the water-soluble methyl etherified melamine formaldehyde resin, 36 g of the acrylate emulsion toughening agent and 18 g of the polyurethane emulsion obtained above are mixed to obtain a water-soluble modified melamine formaldehyde resin. It is used for the impregnation of edge banding paper. It has good flexibility. It is easy to rotate in the edge of furniture (0-180o), the surface coating hardness is H grade (pencil hardness), it can be stored for 6 months at room temperature, residual formaldehyde content. 1.0 Mg/kg.
  • Step 1 Preparation of water-soluble methyl etherified melamine formaldehyde resin:
  • Step 2 Preparation of water-soluble acrylate emulsion toughening agent:
  • Methyl methacrylate 12g, butyl acrylate 30g, acrylic acid 2g, styrene 55g, emulsifier (nonylphenol ethoxylate) 2.5g, initiator (potassium persulfate) 0.8g, the synthesis process is: the above initiator, all Pre-emulsified monomer (99g total) and 2g emulsifier and 100mL deionized water; the remaining 0.5g emulsifier, 50ml deionized water was stirred and dissolved in the reactor and heated to 75oC, pre-emulsified by nitrogen under the protection of nitrogen The liquid was added to the reactor solution for 3 hours, and the temperature was lowered to 65. oC, add water to adjust the pH 8.0, and discharge to room temperature to prepare a water-soluble acrylate emulsion toughening agent.
  • Step 3 Preparation of water-soluble polyurethane emulsion modifier:
  • toluene diisocyanate 180g of polyether, 6g of dimethylolpropionic acid and 9g of ethylenediamine.
  • the synthesis process is as follows: adding toluene diisocyanate, polyether and dimethylolpropionic acid to the reactor at 80 Prepolymerization at oC for 3.5 hours, cooling to 25 oC, emulsification by adding 100 ml of deionized water, adding ethylenediamine chain extension reaction for 1 hour, and discharging to obtain a water-soluble polyurethane emulsion modifier.
  • Step 4 180 g of the water-soluble methyl etherified melamine formaldehyde resin, 54 g of the acrylate emulsion toughening agent and 27 g of the polyurethane emulsion obtained above are mixed to obtain a water-soluble modified melamine formaldehyde resin. It is used for the impregnation of edge banding paper. It has good flexibility. It is easy to rotate in the edge of furniture (0-180o), the surface coating hardness is HB grade (pencil hardness), it can be stored for 6 months at room temperature, residual formaldehyde content. 1.0 mg/kg.
  • Step 1 Preparation of water-soluble methyl etherified melamine formaldehyde resin:
  • Step 2 Preparation of water-soluble acrylate emulsion toughening agent:
  • Step 3 Preparation of water-soluble polyurethane emulsion modifier:
  • Step 4 126 g of the water-soluble methyl etherified melamine formaldehyde resin, 75.6 g of the acrylate emulsion toughening agent and 50.4 g of the polyurethane emulsion modifier are mixed to obtain a water-soluble modified melamine formaldehyde resin. It is used for the impregnation of edge banding paper. It has good flexibility. It is easy to rotate in the edge of furniture (0-180o), the surface coating hardness is H grade (pencil hardness), it can be stored for 6 months at room temperature, residual formaldehyde content. 1.2 Mg/kg.
  • Step 1 Preparation of water-soluble methyl etherified melamine formaldehyde resin:
  • Step 2 Preparation of water-soluble acrylate emulsion toughening agent:
  • Step 3 Preparation of water-soluble polyurethane emulsion modifier:
  • toluene diisocyanate 165g of polyether, 6g of dimethylolpropionic acid and 9g of ethylenediamine.
  • the synthesis process is as follows: adding toluene diisocyanate, polyether and dimethylolpropionic acid to the reactor at 80 The reaction was carried out at oC for 4.0 hours, cooled to 30 ° C, emulsified by adding 100 mL of deionized water, and after 9 g of ethylenediamine was added for chain extension, the reaction was carried out for 1 hour, and a water-soluble polyurethane emulsion modifier was obtained by discharging.
  • Step 4 226.8 g of the water-soluble methyl etherified melamine formaldehyde resin obtained above and 25.2 g of the acrylate emulsion toughening agent are mixed to obtain a water-soluble modified melamine formaldehyde resin. It is used for the impregnation of edge banding paper. It has good flexibility. It is easy to rotate in the edge of furniture (0-180o), the surface coating hardness is HB grade (pencil hardness), it can be stored for 6 months at room temperature, residual formaldehyde content. 1.1 mg/kg.
  • This example differs from Example 4 in that, in step one, an emulsified rosin is added after the methanol etherification reaction. 8g.
  • a water-soluble modified melamine formaldehyde resin was obtained. It is used for the impregnation of edge banding paper. It has good flexibility. It is easy to rotate in the edge of furniture (0-180o), the surface coating hardness is H grade (pencil hardness), it can be stored for 6 months at room temperature, residual formaldehyde content. 1.0 Mg/kg.

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Abstract

本发明公开了一种水溶性改性三聚氰胺甲醛浸渍树脂及其制备方法和应用，其步骤如下：水溶性甲醚化三聚氰胺甲醛树脂采用甲醛和三聚氰胺经加成缩聚反应后，用甲醇醚化后与渗透剂和尿素等除甲醛剂复合即得到；水溶性丙烯酸酯乳液增韧剂采用丙烯酸酯类单体和苯乙烯经乳液聚合法制备；水溶性聚氨酯乳液改性剂采用甲苯二异氰酸酯，聚醚二羟基丙酸和乙二胺经自乳化法制备；三种树脂按一定重量比混合而制成本发明的水溶性改性三聚氰胺甲醛树脂。该树脂可用于家具、造纸行业中如纸封边条和装饰纸的浸渍，具有柔韧性好，残余甲醛含量低，长期稳定等优点。该发明制备工艺简单，避免了有害溶剂挥发扩散带来的危害和污染，实现了绿色生产和节能减排。

Description

水溶性改性三聚氰胺甲醛浸渍树脂及其制备方法和应用
技术领域
本发明涉及一种可用于家具、造纸行业中如纸封边条和装饰纸等制备的水溶性改性三聚氰胺甲醛浸渍树脂及其制备方法，属于家具制造和造纸等领域。
背景技术
三聚氰胺甲醛树脂简称蜜胺树脂为热固性树脂，具有阻燃，耐水、耐热、耐老化、耐电弧、耐化学腐蚀、有良好的绝缘性能、光泽度和机械强度，广泛用于木材家具、塑料、涂料、造纸、纺织、皮革、电气、医药等行业。但其脆性大、储存期短、有机溶剂毒性和挥发性大等缺点限制了它的进一步广泛应用。为此，对其进行改性研究成为当前的热点。
目前对其改性的办法可分为物理改性和化学改性，目的主要是将以往油溶性树脂改为水溶性树脂，降低有机溶剂毒性和挥发性大的缺点，增加韧性、降低甲醛含量和提高树脂稳定性，物理改性主要通过添加一些柔性高分子来增加三聚氰胺甲醛树脂的韧性如用有机硅、聚乙烯醇、聚丙烯酰胺和聚醋酸乙烯酯等而化学改性主要是通过在三聚氰胺甲醛树脂预聚合过程中加入醇类、尿素等可反应分子，提高水溶性，降低甲醛含量，提高树脂稳定性。目前，往往是通过一种改性手段来对树脂进行改性，改性的效果只能达到一种改性目的并且常提高了一方面性能，而又损失了其他的优异性能，如仅加入柔性高分子增韧剂，不能提高树脂的稳定性，常又损失了其表面硬度好耐磨等优异性能。
发明内容
本发明的目的在于克服现有技术的缺点，通过将物理和化学改性方法结合在一起对其进行改性，提供一种兼具良好韧性、低甲醛含量和长期稳定性等综合优异性能的一种水溶性改性三聚氰胺甲醛浸渍树脂及其制备方法。
本发明的上述目的是通过以下技术方案实现的：
一种水溶性改性三聚氰胺甲醛浸渍树脂的制备方法，采用以水溶性甲醚化三聚氰胺甲醛树脂为基体，以水溶性丙烯酸酯乳液和水溶性聚氨酯乳液分别为增韧剂和改性剂，复合制备出的，具体步骤如下：
（1）水溶性甲醚化三聚氰胺甲醛树脂的制备：
原料配方为：按重量百分比计，三聚氰胺30-40%，甲醛20-30%，甲醇40-50%，按上述配比称取甲醛和三聚氰胺，在50-60 oC，PH=8-9的条件下反应30-120分钟，然后升温至80-90 oC ，在PH=6-7的条件下，加入甲醇，反应30-120分钟，即得到水溶性甲醚化三聚氰胺甲醛树脂；
（2）水溶性丙烯酸酯乳液增韧剂的制备：
原料配方为：按重量百分比计，丙烯酸酯类单体36-56%，40-60%苯乙烯，2-3%乳化剂，0.5-1.5%引发剂；将引发剂、上述全部单体（丙烯酸酯类单体和苯乙烯）及部分的乳化剂和去离子水混合进行预乳化；再将剩余的乳化剂用去离子水溶解，在70-80 oC、氮气保护下，将上述单体的预乳化液加入到上述溶解液中反应2-4小时，然后降温至60-70 oC，加入氨水调节 PH=8.0，制得水溶性丙烯酸酯乳液增韧剂；
（3）水溶性聚氨酯乳液改性剂的制备：
原料配方为：按重量百分比计，甲苯二异氰酸酯25-40%，聚醚55-70%，二羟甲基丙酸1-4%，乙二胺3-5%；将甲苯二异氰酸酯、聚醚、二羟甲基丙酸于80 oC下预聚反应3-4小时，降温至10-30 oC下，加入去离子水乳化，加入乙二胺扩链反应1-1.5小时，制得水溶性聚氨酯乳液改性剂；
（4）将上述制得的水溶性甲醚化三聚氰胺甲醛树脂、丙烯酸酯乳液增韧剂和聚氨酯乳液改性剂分别按重量百分比计：50～90％、5～30％和0～20％进行混合，即制得水溶性改性三聚氰胺甲醛树脂。
优选地，按重量百分比计，水溶性甲醚化三聚氰胺甲醛树脂、丙烯酸酯乳液增韧剂和聚氨酯乳液改性剂分别为：50～90％、5～20％和0～10％。
优选地，所述丙烯酸酯类单体为甲基丙烯酸甲酯 10-37%，丙烯酸丁酯54-85% 和0-17%丙烯酸的混合物。
优选地，所述乳化剂为十二烷基硫酸钠和壬基酚聚氧乙烯醚中的一种或两种的混合物。
优选地，所述引发剂为为过硫酸钾和过硫酸铵中的一种或两种的混合物。
优选地，步骤（2）所述预乳化中加入的部分乳化剂为乳化剂总量的10~90%。
优选地，步骤（1）反应最后还加入原料总重量0.05-1%的拉开粉（丁基萘磺酸钠）。
优选地，步骤（1）反应最后还加入原料总重量0.05-5%的尿素或乳化松香。
上述方法制备的水溶性改性三聚氰胺甲醛浸渍树脂用于家具和造纸中的纸封边条和装饰纸的浸渍。
本发明与现有技术相比，具有如下优点：
（1）本发明的水溶性改性三聚氰胺甲醛浸渍树脂具有良好的柔韧性，特别适用于家具和造纸中的纸封边条和装饰纸的浸渍，制备的纸封边条可0-180o任意转角，表面涂层硬度达H级（铅笔硬度），室温下可储存6个月。
（2）本发明的水溶性三聚氰胺甲醛浸渍树脂具有长期的稳定性，可储存3-6个月。
（3）本发明的水溶性改性三聚氰胺甲醛浸渍树脂为环境友好型材料，残余甲醛含量小于国标1.3 mg/kg。改善了以往油溶性浸渍树脂所用有机溶剂毒性和挥发性大、残余甲醛含量高的问题，可环保绿色生产，实现了节能减排。
（4）本发明采用的工艺简单，有利于规模化生产。
附图说明
图1是水溶性甲醚化三聚氰胺甲醛树脂的红外光谱图。
图2是水溶性丙烯酸酯乳液增韧剂的红外光谱图。
图3 是水溶性聚氨酯改性剂的红外光谱图。
具体实施方式
为更好理解本发明，下面结合实施例对本发明做进一步地说明，但是本发明要求保护的范围并不局限于实施例表示的范围。
实施例1
步骤一：水溶性甲醚化三聚氰胺甲醛树脂的制备：
称取三聚氰胺175g，甲醛112.2g，在50 oC下加入反应器中，调整PH=8.5， 反应30分钟，升温至85 oC称量甲醇212g并加入反应器中，调整PH=6.5，反应30分钟后，加入5g尿素降至30oC并加入0.3g拉开粉即可得到所需的水溶性甲醚化三聚氰胺甲醛树脂。
步骤二：水溶性丙烯酸酯乳液增韧剂的制备：
称取甲基丙烯酸甲酯 12g，丙烯酸丁酯30g，丙烯酸2g，苯乙烯54g，乳化剂（十二烷基硫酸钠）2g，引发剂（过硫酸钾）0.6g，其合成工艺方法是：将上述引发剂、全部单体和1.6g乳化剂和100mL去离子水进行预乳化；剩余0.4g乳化剂、50ml去离子水在反应器中搅拌溶解并升温至75oC，在氮气保护下将单体的预乳化液加入到上述反应器溶液中反应3小时，降温至65 oC，加入氨水调节 PH=8.0,降至室温出料即可制得水溶性丙烯酸酯乳液增韧剂。
步骤三：水溶性聚氨酯乳液改性剂的制备：
称取甲苯二异氰酸酯105g，聚醚180g，二羟甲基丙酸6g，乙二胺9g，其合成工艺方法是：将甲苯二异氰酸酯、聚醚、二羟甲基丙酸加入反应器中于80 oC下预聚反应3.5小时，降温至25 oC下，加入100mL去离子水乳化，加入9g乙二胺扩链反应1小时，出料即可制得水溶性聚氨酯乳液改性剂。
步骤四：将上述所得的水溶性甲醚化三聚氰胺甲醛树脂180g、丙烯酸酯乳液增韧剂54g和聚氨酯乳液改性剂18g进行混合，即可制得水溶性改性三聚氰胺甲醛树脂。用于封边条纸的浸渍,其柔韧性好,在家具封边中易转角（0-180o）,表面涂层硬度达H级（铅笔硬度），室温下可储存6个月，残余甲醛含量1.1 mg/kg。
实施例2
步骤一：水溶性甲醚化三聚氰胺甲醛树脂的制备：
称取三聚氰胺175g，甲醛112.2g，在50 oC下加入反应器中,调整PH=8.5, 反应30分钟, 升温至85 oC称量甲醇212g并加入反应器中,调整PH=6.5, 反应30分钟后，加入10g尿素降至室温并加入0.4g拉开粉即可得到所需的水溶性甲醚化三聚氰胺甲醛树脂。
步骤二：水溶性丙烯酸酯乳液增韧剂的制备：
称取甲基丙烯酸甲酯 15g，丙烯酸丁酯27g，丙烯酸2g，苯乙烯55g，乳化剂（十二烷基硫酸钠）2.5 g，引发剂（过硫酸铵）0.6g，其合成工艺方法是：将上述引发剂、全部单体（共99g）和2g乳化剂和100mL去离子水进行预乳化；剩余0.5g乳化剂、50ml去离子水在反应器中搅拌溶解并升温至75oC，在氮气保护下将单体的预乳化液加入到反应器溶液中反应3小时，降温至65 oC，加入氨水调节 PH=8.0,降至室温出料即可制得水溶性丙烯酸酯乳液增韧剂。
步骤三：水溶性聚氨酯乳液改性剂的制备：
称取甲苯二异氰酸酯105g，聚醚180g，二羟甲基丙酸6g，乙二胺9g，其合成工艺方法是：将甲苯二异氰酸酯、聚醚、二羟甲基丙酸加入反应器中于80 oC下预聚反应3.5小时，降温至25 oC下，加入100mL去离子水乳化，加入乙二胺扩链反应1小时，出料即可制得水溶性聚氨酯乳液改性剂。
步骤四：将上述所得的水溶性甲醚化三聚氰胺甲醛树脂180g、丙烯酸酯乳液增韧剂36g和聚氨酯乳液18g进行混合，即可制得水溶性改性三聚氰胺甲醛树脂。用于封边条纸的浸渍,其柔韧性好,在家具封边中易转角（0-180o）,表面涂层硬度达H级（铅笔硬度），室温下可储存6个月，残余甲醛含量1.0 mg/kg。
实施例3
步骤一：水溶性甲醚化三聚氰胺甲醛树脂的制备：
称取三聚氰胺175g，甲醛112.2g，在50 oC下加入反应器中,调整PH=8.5, 反应30分钟, 升温至85 oC称量甲醇212g并加入反应器中,调整PH=6.5, 反应30分钟后，加入8g尿素降至室温并加入0.4g拉开粉即可得到所需的水溶性甲醚化三聚氰胺甲醛树脂。
步骤二：水溶性丙烯酸酯乳液增韧剂的制备：
称取甲基丙烯酸甲酯 12g，丙烯酸丁酯30g，丙烯酸2g，苯乙烯55g，乳化剂（壬基酚聚氧乙烯醚）2.5g，引发剂（过硫酸钾）0.8g，其合成工艺方法是：将上述引发剂、全部单体（共99g）和2g乳化剂和100mL去离子水进行预乳化；剩余0.5g乳化剂、50ml去离子水在反应器中搅拌溶解并升温至75oC，在氮气保护下将单体的预乳化液加入到反应器溶液中反应3小时，降温至65 oC，加入氨水调节 PH=8.0,降至室温出料即可制得水溶性丙烯酸酯乳液增韧剂。
步骤三：水溶性聚氨酯乳液改性剂的制备：
称取甲苯二异氰酸酯105g，聚醚180g，二羟甲基丙酸6g，乙二胺9g，其合成工艺方法是：将甲苯二异氰酸酯、聚醚、二羟甲基丙酸加入反应器中于80 oC下预聚反应3.5小时，降温至25 oC下，加入100ml 去离子水乳化，加入乙二胺扩链反应1小时，出料即可制得水溶性聚氨酯乳液改性剂。
步骤四：将上述所得的水溶性甲醚化三聚氰胺甲醛树脂180g、丙烯酸酯乳液增韧剂54g和聚氨酯乳液27g进行混合，即可制得水溶性改性三聚氰胺甲醛树脂。用于封边条纸的浸渍,其柔韧性好,在家具封边中易转角（0-180o）,表面涂层硬度达HB级（铅笔硬度），室温下可储存6个月，残余甲醛含量1.0mg/kg。
实施例4
步骤一：水溶性甲醚化三聚氰胺甲醛树脂的制备：
称取三聚氰胺150g，甲醛100g ，在50 oC下加入反应器中，调整PH=8.0， 反应30分钟，升温至80 oC称量甲醇249.6g并加入反应器中，调整PH=6.0，反应60分钟后，即可得到所需的水溶性甲醚化三聚氰胺甲醛树脂。
步骤二：水溶性丙烯酸酯乳液增韧剂的制备：
称取甲基丙烯酸甲酯 6g，丙烯酸丁酯30g，苯乙烯60g，乳化剂（十二烷基硫酸钠）3g，引发剂（过硫酸钾）1.0g，其合成工艺方法是：将上述引发剂、全部单体和2g乳化剂和100mL去离子水进行预乳化；剩余1g乳化剂、50ml去离子水在反应器中搅拌溶解并升温至70oC，在氮气保护下将单体的预乳化液加入到上述反应器溶液中反应2小时，降温至60 oC，加入氨水调节 PH=8.0,降至室温出料即可制得水溶性丙烯酸酯乳液增韧剂。
步骤三：水溶性聚氨酯乳液改性剂的制备：
称取甲苯二异氰酸酯75g，聚醚210g，二羟甲基丙酸3g，乙二胺12g，其合成工艺方法是：将甲苯二异氰酸酯、聚醚、二羟甲基丙酸加入反应器中于80 oC下预聚反应3.0小时，降温至10 oC下，加入100mL去离子水乳化，加入12g乙二胺扩链反应1.5小时，出料即可制得水溶性聚氨酯乳液改性剂。
步骤四：将上述所得的水溶性甲醚化三聚氰胺甲醛树脂126g、丙烯酸酯乳液增韧剂75.6g和聚氨酯乳液改性剂50.4g进行混合，即可制得水溶性改性三聚氰胺甲醛树脂。用于封边条纸的浸渍,其柔韧性好,在家具封边中易转角（0-180o）,表面涂层硬度达H级（铅笔硬度），室温下可储存6个月，残余甲醛含量1.2 mg/kg。
实施例5
步骤一：水溶性甲醚化三聚氰胺甲醛树脂的制备：
称取三聚氰胺175g，甲醛125g，在50 oC下加入反应器中，调整PH=9.0， 反应30分钟，升温至90 oC称量甲醇200g并加入反应器中，调整PH=7.0，反应120分钟后，即可得到所需的水溶性甲醚化三聚氰胺甲醛树脂。
步骤二：水溶性丙烯酸酯乳液增韧剂的制备：
称取甲基丙烯酸甲酯 15g，丙烯酸丁酯35g，丙烯酸6g，苯乙烯40g，乳化剂（壬基酚聚氧乙烯醚）2.5g，引发剂（过硫酸钾）1.5g，其合成工艺方法是：将上述引发剂、全部单体和2g乳化剂和100mL去离子水进行预乳化；剩余0.5g乳化剂、50ml去离子水在反应器中搅拌溶解并升温至80oC，在氮气保护下将单体的预乳化液加入到上述反应器溶液中反应4小时，降温至70 oC，加入氨水调节 PH=8.0,降至室温出料即可制得水溶性丙烯酸酯乳液增韧剂。
步骤三：水溶性聚氨酯乳液改性剂的制备：
称取甲苯二异氰酸酯120g，聚醚165g，二羟甲基丙酸6g，乙二胺9g，其合成工艺方法是：将甲苯二异氰酸酯、聚醚、二羟甲基丙酸加入反应器中于80 oC下反应4.0小时，降温至30 oC下，加入100mL去离子水乳化，加入9g乙二胺扩链后，反应1小时，出料即可制得水溶性聚氨酯乳液改性剂。
步骤四：将上述所得的水溶性甲醚化三聚氰胺甲醛树脂226.8g和丙烯酸酯乳液增韧剂25.2g进行混合，即可制得水溶性改性三聚氰胺甲醛树脂。用于封边条纸的浸渍,其柔韧性好,在家具封边中易转角（0-180o），表面涂层硬度达HB级（铅笔硬度），室温下可储存6个月，残余甲醛含量1.1mg/kg。
实施例6
本实施例与实施例4的不同之处在于：在步骤一，在甲醇醚化反应后加入了乳化松香 8g。本实施例制得水溶性改性三聚氰胺甲醛树脂。用于封边条纸的浸渍,其柔韧性好,在家具封边中易转角（0-180o）,表面涂层硬度达H级（铅笔硬度），室温下可储存6个月，残余甲醛含量1.0 mg/kg。

Claims (10)

  1. 一种水溶性改性三聚氰胺甲醛浸渍树脂的制备方法，其特征在于，
    包括如下步骤：
    （1） 水溶性甲醚化三聚氰胺甲醛树脂的制备：
    原料配方为：按重量百分比计，三聚氰胺30-40%，甲醛20-30%，甲醇40-50%，按上述配比称取甲醛和三聚氰胺，在50-60 oC，PH=8-9的条件下反应30-120分钟，然后升温至80-90 oC ，在PH=6-7的条件下，加入甲醇，反应30-120分钟，即得到水溶性甲醚化三聚氰胺甲醛树脂；
    （2）水溶性丙烯酸酯乳液增韧剂的制备：
    原料配方为：按重量百分比计，丙烯酸酯类单体36-56%，苯乙烯40-60%，乳化剂2-3%，引发剂0.5-1.5%；将引发剂、上述全部单体及部分的乳化剂和去离子水混合进行预乳化；再将剩余的乳化剂用去离子水溶解，在70-80 oC、氮气保护下，将上述单体的预乳化液加入到上述溶解液中反应2-4小时，然后降温至60-70 oC，加入氨水调节 PH=8.0，制得水溶性丙烯酸酯乳液增韧剂；
    （3）水溶性聚氨酯乳液改性剂的制备：
    原料配方为：按重量百分比计，甲苯二异氰酸酯25-40%，聚醚55-70%，二羟甲基丙酸1-4%，乙二胺3-5%；将甲苯二异氰酸酯、聚醚、二羟甲基丙酸于80 oC下预聚反应3-4小时，降温至10-30 oC下，加入去离子水乳化，加入乙二胺扩链反应1-1.5小时，制得水溶性聚氨酯乳液改性剂；
    （4）将上述制得的水溶性甲醚化三聚氰胺甲醛树脂、丙烯酸酯乳液增韧剂和聚氨酯乳液改性剂分别按重量百分比计：50～90％、5～30％和0～20％进行混合，即制得水溶性改性三聚氰胺甲醛树脂。
  2. 根据权利要求1所述的制备方法，其特征在于，按重量百分比计，水溶性甲醚化三聚氰胺甲醛树脂、丙烯酸酯乳液增韧剂和聚氨酯乳液改性剂分别为：50～90％、5～20％和0～10％。
  3. 根据权利要求2所述的制备方法，其特征在于，所述丙烯酸酯类单体为甲基丙烯酸甲酯 10-37%，丙烯酸丁酯54-85% 和0-17%丙烯酸的混合物。
  4. 根据权利要求3所述的制备方法，其特征在于，所述乳化剂为十二烷基硫酸钠和壬基酚聚氧乙烯醚中的一种或两种的混合物。
  5. 根据权利要求4所述的制备方法，其特征在于，所述引发剂为过硫酸钾和过硫酸铵中的一种或两种的混合物。
  6. 根据权利要求1或2或3或4或5所述的制备方法，其特征在于，步骤（2）所述预乳化中加入的部分乳化剂为乳化剂总量的10~90%。
  7. 根据权利要求6所述的制备方法，其特征在于，步骤（1）反应最后还加入原料总重量0.05-1%的拉开粉。
  8. 根据权利要求7所述的制备方法，其特征在于，步骤（1）反应最后还加入原料总重量0.05-5%的尿素或乳化松香。
  9. 一种水溶性改性三聚氰胺甲醛浸渍树脂，其特征在于，该树脂是由权利要求1~8任意一项所述的方法制备的。
  10. 权利要求9所述的水溶性改性三聚氰胺甲醛浸渍树脂的应用，其特征在于，该树脂用于家具和造纸中的纸封边条和装饰纸的浸渍。
PCT/CN2011/084796 2011-08-05 2011-12-28 水溶性改性三聚氰胺甲醛浸渍树脂及其制备方法和应用 Ceased WO2013020344A1 (zh)

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