CN110643312B - 一种环保型酚醛胶黏剂的制备方法 - Google Patents
一种环保型酚醛胶黏剂的制备方法 Download PDFInfo
- Publication number
- CN110643312B CN110643312B CN201911050971.6A CN201911050971A CN110643312B CN 110643312 B CN110643312 B CN 110643312B CN 201911050971 A CN201911050971 A CN 201911050971A CN 110643312 B CN110643312 B CN 110643312B
- Authority
- CN
- China
- Prior art keywords
- parts
- adhesive
- formaldehyde
- chitosan
- cooling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001661 Chitosan Polymers 0.000 claims abstract description 23
- 229920001864 tannin Polymers 0.000 claims abstract description 21
- 235000018553 tannin Nutrition 0.000 claims abstract description 21
- 239000001648 tannin Substances 0.000 claims abstract description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 18
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229930003836 cresol Natural products 0.000 claims abstract description 14
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 13
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 9
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 8
- 239000000440 bentonite Substances 0.000 claims abstract description 7
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 108010073771 Soybean Proteins Proteins 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- 235000019710 soybean protein Nutrition 0.000 abstract 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical class C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明公开了一种环保型酚醛胶黏剂及其制备方法，单宁、壳聚糖、甲酚、氢氧化钠、亚硫酸钠、亚硫酸钙、甲醛、三聚氰胺和膨润土作为主要原料；其所用原料主要用量为5‑10份单宁、10‑15份壳聚糖、3‑5份甲酚、1‑3份氢氧化钠、0.1‑1份亚硫酸钠、0.1‑1份亚硫酸、三聚氰胺0.1‑0.5份，甲醛2‑5份、膨润土1‑2份；本发明的方法制备获得的一种大豆蛋白基无醛胶黏剂及其制备方法,相对于传统酚醛胶黏剂，使用单宁和壳聚糖取代大量甲酚，减少了产品中游离酚的产生，通过化学反应和物理吸附的方法双重抑制游离甲醛的释放，使得胶黏剂甲醛释放量大幅降低，胶黏强度高，稳定性增强。
Description
技术领域
本发明本发明涉及一种环保型酚醛胶黏剂的制备方法，属于胶黏剂技术领域。
背景技术
酚醛树脂胶黏剂是酚类与醛类在催化剂作用下形成的。它是工业化最早(1910年，德国Bakelite)的合成高分子材料。由于酚醛树脂具有制造工艺简单，原料价格低廉，产品胶接强度大等优点，成为林产品加工制品中不可缺少的胶黏剂材料之一。但酚醛树脂在制备过程中固化温度过高，且成品中含有大量的游离酚和游离醛，这些问题对酚醛树脂的应用范围和成品质量产生了一定程度的影响。专利CN108345160A提供了一种环保型胶黏剂及其制备方法。使用酚醛环氧树脂和酚酮树脂复合添加了阻燃剂、消泡剂、稳定剂和交联剂，通过升温搅拌混合得到的环保型胶黏剂，具有较好的耐热性，但原料较多，成本较高，产品含有大量残留酚和醛，限制了其工业的应用。CN106750065A提供一种改性酚醛树脂胶黏剂。使用了氰胺化合物、桐油酸酯、氧化淀粉和单宁作为改性剂降低酚醛残留量，提高胶黏强度。而普通改性条件下，改性剂与甲醛反应速度过快，胶粘剂生活期短，单宁分子为环状结构，因立体障碍。分子连接密度小，耐水性较差。专利CN108949078A提供一种改性酚醛树脂胶黏剂的方法。在酚醛树脂中加入木质素降低了成本和有害物质的释放，由于木质素分子量大小不一，分散不均，胶黏剂的稳定性较差，储存时间短，胶层颜色较深。
发明内容
本发明的目的在于提供一种环保型酚醛胶黏剂及其制备方法,通过该方法制备的胶黏剂甲醛释放低，胶黏强度高，稳定性好。
一种环保型酚醛胶黏剂的制备方法，其特征在于该方法包括以下步骤：
步骤1、室温下，在装有电动搅拌机、温度计和冷凝管的四口烧瓶中加入5份单宁、13份壳聚糖、3份甲酚、2.5份氢氧化钠、0.6份亚硫酸钠，0.6份亚硫酸钙与5份水，搅拌均匀10min，然后进行超声处理20min；
步骤2、缓慢升温至95-98℃，恒温加热回流2.5h，加入2.5份水搅拌15min之后冷却至40℃，得到超声液化预混物；
步骤3、向上述预混物中加入3份甲醛升温至88-90℃，10min内逐渐加入浓度30%的NaOH溶液，调节PH=8.5，反应40min；
步骤4、温度降至83℃,依次加入0.3份三聚氰胺、3份甲醛，温度稳定后30min内逐渐加入浓度30%的NaOH溶液，调节PH=8.5，控制温度85-90℃，反应70min；
步骤5、温度降至84℃，继续加入3份甲醛，20min内逐渐加入浓度30%的NaOH溶液，调节PH=8.5，85-90℃反应60min，随后降温至40℃以下出料；
步骤6、向上述出料中加入1份壳聚糖和4份浓度12%的醋酸溶液和4份甲氧基聚乙二醇，室温下持续搅拌15min，转移至烧杯中用浓度30%的NaOH溶液，调节至中性；
步骤7、向上述中性混合液中加入1份膨润土，制成悬浊液，50℃下超声处理20min，随后冷却至室温，减压抽滤，用蒸馏水洗涤至中性，干燥过夜，即得环保型高分子聚合胶黏剂。
有益效果：本发明提供了一种环保型高分子聚合胶黏剂及其制备方法,利用单宁和壳聚糖为原料在碱性条件下与甲醛缩聚形成了高分子聚合的热固性树脂胶黏剂材料，相对于传统酚醛胶黏剂，使用单宁和壳聚糖取代大量甲酚，减少了产品中游离酚的产生，三聚氰胺分子通过化学反应进入了树脂的合成体系内，使得树脂体系颜色变浅的同时，三嗪环的结构也增加了树脂体系的强度，其分子环状结构上的羟甲基官能团使得树脂成为环状或者链状的大分子基团。制备过程中利用超声处理，在超声波的空穴作用，在溶液中产生真空微气泡，该气泡的冲击力作用于壳聚糖和单宁的表面和缝隙内，对其产生一定的剪切作用，从而使其氢键断裂，从而达到一定的降解和活化作用。当胶黏剂作用于木材时，可以少量的膨润土填充并结合在高分子聚合物未作用的木材表面的孔隙当中，增加了胶黏剂与木材的接触面积，抑制胶体流动，加快固化速率，经过壳聚糖氨基与游离甲醛的羰基反应，部分释放出的甲醛也能通过膨润土物理吸附的方式进一步被消除，从而实现胶黏剂中对甲醛释放的双重抑制。
具体实施方式
实施例1
一种环保型酚醛胶黏剂的制备方法，其特征在于该方法包括以下步骤：
步骤1、室温下，在装有电动搅拌机、温度计和冷凝管的四口烧瓶中加入5份单宁、13份壳聚糖、3份甲酚、2.5份氢氧化钠、0.6份亚硫酸钠，0.6份亚硫酸钙与5份水，搅拌均匀10min，然后进行超声处理20min；
步骤2、缓慢升温至95-98℃，恒温加热回流2.5h，加入2.5份水搅拌15min之后冷却至40℃，得到超声液化预混物；
步骤3、向上述预混物中加入3份甲醛升温至90℃，10min内逐渐加入浓度30%的NaOH溶液，调节PH=8.5，反应40min；
步骤4、温度降至83℃,依次加入0.3份三聚氰胺、3份甲醛，温度稳定后30min内逐渐加入浓度30%的NaOH溶液，调节PH=8.5，控制温度85-90℃，反应70min；
步骤5、温度降至84℃，继续加入3份甲醛，20min内逐渐加入浓度30%的NaOH溶液，调节PH=8.5，90℃反应60min，随后降温至40℃以下出料；
步骤6、向上述出料中加入1份壳聚糖和4份浓度12%的醋酸溶液和4份甲氧基聚乙二醇，室温下持续搅拌15min，转移至烧杯中用浓度30%的NaOH溶液，调节至中性；
步骤7、向上述中性混合液中加入1份膨润土，制成悬浊液，50℃下超声处理20min，随后冷却至室温，减压抽滤，用蒸馏水洗涤至中性，干燥过夜，即得环保型高分子聚合胶黏剂。
实施例2
步骤1、室温下，在装有电动搅拌机、温度计和冷凝管的四口烧瓶中加入5份单宁、7份壳聚糖、3份甲酚、2.5份氢氧化钠、0.6份亚硫酸钠，0.6份亚硫酸钙与5份水，搅拌均匀10min，然后进行超声处理20min；其余制备和实施例1相同。
实施例3
步骤1、室温下，在装有电动搅拌机、温度计和冷凝管的四口烧瓶中加入5份单宁、1份壳聚糖、3份甲酚、2.5份氢氧化钠、0.6份亚硫酸钠，0.6份亚硫酸钙与5份水，搅拌均匀10min，然后进行超声处理20min；其余制备和实施例1相同。
实施例4
步骤1、室温下，在装有电动搅拌机、温度计和冷凝管的四口烧瓶中加入10份单宁、1份壳聚糖、3份甲酚、2.5份氢氧化钠、0.6份亚硫酸钠，0.6份亚硫酸钙与5份水，搅拌均匀10min，然后进行超声处理20min；其余制备和实施例1相同。
实施例5
步骤1、室温下，在装有电动搅拌机、温度计和冷凝管的四口烧瓶中加入1份单宁、13份壳聚糖、3份甲酚、2.5份氢氧化钠、0.6份亚硫酸钠，0.6份亚硫酸钙与5份水，搅拌均匀10min，然后进行超声处理20min；其余制备和实施例1相同。
对照例1
与实施例1不同点在于：胶黏剂制备的步骤1中，用等量的甲酚取代单宁，其余步骤与实施例1完全相同。
对照例2
与实施例1不同点在于：胶黏剂制备的步骤1中，等量的甲酚取代壳聚糖，其余步骤与实施例1完全相同。
将以上实施例和对照例制备得到的胶黏剂进行性能测试,以桉木单板为基材制备三层胶合板，施胶量400 份/m2(双面)；涂胶后室温闭合陈放20min，再送入平板硫化机，单位压力1.2 MPa下常温预压20min，在140℃条件下热压，单位热压压力1.2MPa，热压时间为70s/mm。胶合强度按照国家标准GB/T 17657-2013中《人造板及饰面人造板理化性能试验方法》测定胶合强度和甲醛释放量。检测结果如下：
实验结果表明本发明提供的环保型酚醛胶黏剂具有很好的胶合强度，胶黏剂材料在标准测试条件下，胶合强度一定，游离酚和甲醛释放量越低，说明对环境的污染越小越好，使用越安全，反之，污染越大，对人体的危害越大；与实施例1相比，实施例2到实施例5，分别改变胶黏剂中主要原料单宁和壳聚糖的配比，对材料的胶合强度影响不大，但是游离酚的量明显增加，并且甲醛的释放量是实施例1的3-4倍，说明单宁和壳聚糖的配比在5:13时，对有机污染物的抑制效果最好；对照例1至对照例2不再加入壳聚糖和单宁，用传统的甲酚取代，尽管胶合强度略有提高，但是游离酚和甲醛释放量出现明显升高，对环境的污染较大，危险性较高。
Claims (1)
1.一种环保型酚醛胶黏剂，其特征在于，该胶黏剂的制备方法包括以下步骤：
步骤1、室温下，在装有电动搅拌机、温度计和冷凝管的四口烧瓶中加入5份单宁、13份壳聚糖、3份甲酚、2.5份氢氧化钠、0.6份亚硫酸钠，0.6份亚硫酸钙与5份水，搅拌均匀10min，然后进行超声处理20min；
步骤2、缓慢升温至95-98℃，恒温加热回流2.5h，加入2.5份水搅拌15min之后冷却至40℃，得到超声液化预混物；
步骤3、向上述预混物中加入3份甲醛升温至90℃，10min内逐渐加入浓度30%的NaOH溶液，调节pH=8.5，反应40min；
步骤4、温度降至83℃,依次加入0.3份三聚氰胺、3份甲醛，温度稳定后30min内逐渐加入浓度30%的NaOH溶液，调节pH=8.5，控制温度85-90℃，反应70min；
步骤5、温度降至84℃，继续加入3份甲醛，20min内逐渐加入浓度30%的NaOH溶液，调节pH=8.5，90℃反应60min，随后降温至40℃以下出料；
步骤6、向上述出料中加入1份壳聚糖和4份浓度12%的醋酸溶液和4份甲氧基聚乙二醇，室温下持续搅拌15min，转移至烧杯中用浓度30%的NaOH溶液，调节至中性；
步骤7、向上述中性混合液中加入1份膨润土，制成悬浊液，50℃下超声处理20min，随后冷却至室温，减压抽滤，用蒸馏水洗涤至中性，干燥过夜，即得环保型酚醛胶黏剂。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911050971.6A CN110643312B (zh) | 2019-10-31 | 2019-10-31 | 一种环保型酚醛胶黏剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911050971.6A CN110643312B (zh) | 2019-10-31 | 2019-10-31 | 一种环保型酚醛胶黏剂的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110643312A CN110643312A (zh) | 2020-01-03 |
| CN110643312B true CN110643312B (zh) | 2021-07-09 |
Family
ID=68995219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911050971.6A Active CN110643312B (zh) | 2019-10-31 | 2019-10-31 | 一种环保型酚醛胶黏剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110643312B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763489A (zh) * | 2020-05-29 | 2020-10-13 | 安徽老石人石业有限公司 | 一种天然花岗岩大理石与多种人造材料复合高强度粘接剂 |
| CN112677274A (zh) * | 2020-12-16 | 2021-04-20 | 临泉县四红木业有限公司 | 一种新型强化地板的热压工艺 |
| CN114311502B (zh) * | 2021-12-17 | 2024-01-30 | 浙江安胜科技股份有限公司 | 一种高精度钢圈包胶用加工工艺 |
| CN114891278B (zh) * | 2022-06-13 | 2023-05-16 | 西南林业大学 | 一种全生物质基建筑材料及其制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911093A (zh) * | 2014-04-29 | 2014-07-09 | 西北大学 | 一种糖酚类树脂胶黏剂的制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036238B2 (ja) * | 1982-04-14 | 1985-08-19 | 住友ベークライト株式会社 | 木材用粉末樹脂接着剤の製造方法 |
| CN102061141B (zh) * | 2009-11-11 | 2013-10-16 | 青岛生物能源与过程研究所 | 木质素基木材用环保胶粘剂的制备方法 |
| CN106750065A (zh) * | 2016-11-30 | 2017-05-31 | 黄河三角洲京博化工研究院有限公司 | 一种改性酚醛树脂胶黏剂 |
| CN109304787A (zh) * | 2018-11-07 | 2019-02-05 | 广西横县丽冠人造板有限责任公司 | 一种防火阻燃型中密度纤维衣柜专用板的生产方法 |
-
2019
- 2019-10-31 CN CN201911050971.6A patent/CN110643312B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911093A (zh) * | 2014-04-29 | 2014-07-09 | 西北大学 | 一种糖酚类树脂胶黏剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110643312A (zh) | 2020-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110643312B (zh) | 一种环保型酚醛胶黏剂的制备方法 | |
| JP7511485B2 (ja) | 結合用樹脂を調製するためのプロセス | |
| EP2904061B1 (en) | Modified polyphenol binder compositions and methods for making and using same | |
| CN108641673B (zh) | 一种无甲醛释放胶合板的制备方法 | |
| CA2832108C (en) | A method for producing a binder composition, a binder composition, an adhesive composition, a layered composite structure, and uses of the binder composition and the adhesive composition | |
| CA2867391A1 (en) | Adhesive compositions having a reduced cure time and methods for making and using same | |
| JP7644032B2 (ja) | 結合樹脂を調製する方法 | |
| CA2902930C (en) | Binder compositions that include a polyphenolic compound, an unsaturated compound, and a free radical precursor, and methods for making and using same | |
| EP3781642B1 (en) | Process for preparing a bonding resin | |
| CN109679578B (zh) | 一种韧性豆粕蛋白胶黏剂及其制备方法 | |
| Dunky | Natural Crosslinkers for Naturally‐Based Adhesives | |
| SE545325C2 (en) | Process for the preparation of a bonding resin | |
| WO2021124127A1 (en) | Novel process for preparing a bonding resin | |
| WO2022003614A1 (en) | Method for preparing a bonding resin | |
| Pizzi | Wood/bark extracts as adhesives and preservatives | |
| Kawalerczyk et al. | Microcellulose as a modifier for UF and PF resins allowing the reduction of adhesive application in plywood manufacturing | |
| CN110734723A (zh) | 一种木质工艺品强力粘合剂及其制备方法 | |
| WO2024134449A1 (en) | Improved bonding resin | |
| CN117327242A (zh) | 一种enf级人造板用改性酚醛树脂及其制备方法 | |
| SE545917C2 (en) | Bonding resin comprising lignin | |
| CN119351013A (zh) | 一种单宁酸修饰的木质素酚醛树脂抗菌胶黏剂及其制备方法 | |
| CN119384478A (zh) | 改善的粘合树脂 | |
| RU2022100403A (ru) | Композиция смолы |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210624 Address after: 518000 Room 301, 401 (3-4 / F), building C, Abao Science Park, 3 shunu Road, Jutang community, Fucheng street, Longhua District, Shenzhen City, Guangdong Province Applicant after: Shenzhen anbos science and Technology Co.,Ltd. Address before: 221000 No.9 University Pioneer Park, Xuzhou high tech Industrial Development Zone, Xuzhou City, Jiangsu Province Applicant before: XUZHOU SHUNPING BIOTECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |