CN114836153A - A kind of preparation method of blending modified resin adhesive - Google Patents
A kind of preparation method of blending modified resin adhesive Download PDFInfo
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- CN114836153A CN114836153A CN202210596616.4A CN202210596616A CN114836153A CN 114836153 A CN114836153 A CN 114836153A CN 202210596616 A CN202210596616 A CN 202210596616A CN 114836153 A CN114836153 A CN 114836153A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 52
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 52
- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000002156 mixing Methods 0.000 title claims abstract description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000000243 solution Substances 0.000 claims abstract description 86
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229920005551 calcium lignosulfonate Polymers 0.000 claims abstract description 52
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims abstract description 52
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012527 feed solution Substances 0.000 claims description 6
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 claims description 4
- 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 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 229920005610 lignin Polymers 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 229920001568 phenolic resin Polymers 0.000 description 9
- 239000004375 Dextrin Substances 0.000 description 8
- 229920001353 Dextrin Polymers 0.000 description 8
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 8
- 235000019425 dextrin Nutrition 0.000 description 8
- 235000013312 flour Nutrition 0.000 description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000002023 wood Substances 0.000 description 7
- 229920001807 Urea-formaldehyde Polymers 0.000 description 6
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- VJOCYCQXNTWNGC-UHFFFAOYSA-L calcium;benzenesulfonate Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 VJOCYCQXNTWNGC-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明公开了一种共混改性树脂胶粘剂的制备方法，属于复合材料技术领域。其包括以下的操作步骤：准备木质素磺酸钙与丙烯酸溶液；将木质素磺酸钙与乙酸乙酯混合，并将丙烯酸溶液与4‑氯‑3,5‑二甲基苯酚进行混合，木质素磺酸钙与乙酸乙酯的混合液进行过滤，获取木质素磺酸钙的乙酸乙酯溶液，同时，丙烯酸溶液与4‑氯‑3,5‑二甲基苯酚的混合液的pH值调整至8；准备甲醛溶液，接着加入所有的尿素，充分搅拌，得到料液，然后开始升值至90℃，逐滴加入得到的木质素磺酸钙的乙酸乙酯溶液，接着逐滴加入得到的丙烯酸溶液与4‑氯‑3,5‑二甲基苯酚的混合液，并加入氧化铝颗粒，最后降温至室温，出料经测试，具有较高的黏度、胶接强度及阻燃能力。
The invention discloses a preparation method of a blended modified resin adhesive, which belongs to the technical field of composite materials. It includes the following operation steps: preparing calcium lignosulfonate and acrylic acid solution; mixing calcium lignosulfonate and ethyl acetate, mixing acrylic acid solution with 4-chloro-3,5-dimethylphenol, and lignin The mixed solution of calcium sulfonate and ethyl acetate is filtered to obtain the ethyl acetate solution of calcium lignosulfonate, and meanwhile, the pH value of the mixed solution of acrylic acid solution and 4-chloro-3,5-dimethylphenol is adjusted To 8; prepare the formaldehyde solution, then add all the urea, fully stir to obtain the feed liquid, then start to rise to 90 ° C, add dropwise the obtained ethyl acetate solution of calcium lignosulfonate, and then dropwise add the obtained acrylic acid A mixture of the solution and 4-chloro-3,5-dimethylphenol, and alumina particles are added, and finally cooled to room temperature. The discharge has been tested and has high viscosity, bonding strength and flame retardant ability.
Description
技术领域technical field
本发明属于复合材料技术领域，具体地说，涉及一种改进的改性树脂胶粘剂。The invention belongs to the technical field of composite materials, in particular to an improved modified resin adhesive.
背景技术Background technique
自1844年首次合成脲醛树脂(UF)胶粘剂以来，UF胶粘剂的使用量不断增大，并且已成为人造板的主要胶种之一(占总用量的90％以上)，也是木材工业使用量最大的胶粘剂(占总消耗量的60％以上)。人造板的污染主要来自于胶粘剂，由UF胶粘剂胶接而成的木制品会不断释放出游离F(甲醛)，故各国针对F释放量的问题制定了系列的法律法规。国内的GB/T 18580—2001《室内装饰装修材料人造板及其制品中甲醛释放限量》强制性标准限量规定了人造板生产企业用UF胶粘剂的低F释放指标，而美国加州CARB法规对板材的F释放量之限量指标比国内标准提高了70多倍(这对国内木材加工业来说是一个挑战，同时也是一个难得的机遇)。因此，降低UF胶粘剂及其相关制品的游离F释放量已迫在眉睫。Since the first synthesis of urea-formaldehyde resin (UF) adhesives in 1844, the usage of UF adhesives has been increasing, and it has become one of the main types of wood-based panels (accounting for more than 90% of the total usage), and it is also the largest used in the wood industry. Adhesives (over 60% of total consumption). The pollution of wood-based panels mainly comes from adhesives. Wood products glued with UF adhesives will continuously release free F (formaldehyde). Therefore, various countries have formulated a series of laws and regulations on the issue of F release. The domestic GB/T 18580-2001 "Limited Formaldehyde Emission Limits in Wood-based Panels and Products of Interior Decoration Materials" is a mandatory standard limit that specifies the low F emission index of UF adhesives used by wood-based panel manufacturers. The limit index of F release is more than 70 times higher than the domestic standard (this is a challenge for the domestic wood processing industry, and it is also a rare opportunity). Therefore, it is urgent to reduce the free F release of UF adhesives and related products.
现有发明专利，其公开号为CN104162624B，公开一种壳型粘合用的专用胶水及其配制工艺，其技术方案如下：The existing invention patent, whose publication number is CN104162624B, discloses a special glue for shell type bonding and its preparation process, and its technical scheme is as follows:
“一种壳型粘合用的专用胶水，由酚醛树脂、乌洛托品、糊精、面粉和水组成，且各组分按重量百分比计含量分别为酚醛树脂25％，乌洛托品15％，糊精10％，面粉20％，水30％。"A special glue for shell-type bonding, which is composed of phenolic resin, urotropine, dextrin, flour and water, and the content of each component by weight is 25% of phenolic resin, 15% of urotropine. %, dextrin 10%, flour 20%, water 30%.
一种壳型粘合用的专用胶水配制工艺，依次包括以下步骤：A special glue preparation process for shell type bonding, comprising the following steps in turn:
1)将原材料酚醛树脂、乌洛托品、糊精、面粉进行分类堆放于干燥处，并作好标识，存放期温度要求≤30°；1) The raw materials, phenolic resin, urotropine, dextrin, and flour, should be classified and stacked in a dry place, and marked well, and the storage period temperature should be less than or equal to 30°;
2)精确按照酚醛树脂25％，乌洛托品15％，糊精10％，面粉20％，水30％的重量百分比进行称量；2) Weigh accurately according to the weight percentages of 25% phenolic resin, 15% urotropine, 10% dextrin, 20% flour, and 30% water;
3)配制的时候，将按重量百分比称量好的原材料酚醛树脂、乌洛托品、糊精、面粉均匀的混合在一起，然后将混合好的原材料酚醛树脂、乌洛托品、糊精、面粉进行分批，然后一批一批放入重量百分比为30％的水中，待每批原材料酚醛树脂、乌洛托品、糊精、面粉搅拌均匀后再放入第二批，以此类推，直至将全部原材料酚醛树脂、乌洛托品、糊精、面粉放入水中为止；3) When preparing, mix the raw materials phenolic resin, urotropine, dextrin, and flour that are weighed in percentage by weight evenly, and then mix the mixed raw materials phenolic resin, urotropine, dextrin, The flour is divided into batches, and then put into 30% water by weight in batches. After each batch of raw materials such as phenolic resin, urotropine, dextrin, and flour are evenly mixed, the second batch is added, and so on. Until all raw materials phenolic resin, urotropine, dextrin, flour are put into water;
4)观察搅拌均匀后的胶水，要求无颗粒，无粉状现象产生；4) Observe the glue after stirring evenly, requiring no particles and no powdery phenomenon;
5)将步骤4)后的胶水，再根据使用要求调配稀稠程度”。5) The glue after step 4), and then adjust the degree of thinness according to the requirements of use".
综合分析来看，经分析其黏度、固化时间及胶粘强度等参数均低于本申请，且本申请还具备阻燃效果。From a comprehensive analysis, the parameters such as viscosity, curing time and adhesive strength are all lower than those of the present application, and the present application also has a flame retardant effect.
发明内容SUMMARY OF THE INVENTION
1、要解决的问题1. The problem to be solved
针对上述现有技术存在的问题，本发明提供一种共混改性树脂胶粘剂的制备方法，经测试，具有较高的黏度、胶接强度及阻燃能力，经猜测，木质素磺酸钙可能还起到隔热包覆作用，额外的实验(未提供)表明，直至330℃左右才出现初步氧化分解现象，570℃左右发生中期氧化燃烧，790℃发生后期氧化燃烧。In view of the problems existing in the above-mentioned prior art, the present invention provides a preparation method of a blended modified resin adhesive. After testing, it has higher viscosity, bonding strength and flame retardant ability. After speculation, calcium lignosulfonate may be It also plays the role of thermal insulation coating. Additional experiments (not provided) show that the initial oxidative decomposition phenomenon does not occur until about 330 °C, the middle-stage oxidative combustion occurs at about 570 °C, and the late oxidative combustion occurs at 790 °C.
2、技术方案2. Technical solutions
为解决上述问题，本发明采用如下的技术方案。In order to solve the above problems, the present invention adopts the following technical solutions.
一种共混改性树脂胶粘剂的制备方法，包括以下的操作步骤：A preparation method of a blended modified resin adhesive, comprising the following operation steps:
准备木质素磺酸钙与丙烯酸溶液；Prepare calcium lignosulfonate and acrylic acid solution;
将木质素磺酸钙与乙酸乙酯第一次混合，并将丙烯酸溶液与4-氯-3,5-二甲基苯酚进行第二次混合，接着，木质素磺酸钙与乙酸乙酯的混合液进行过滤，获取木质素磺酸钙的乙酸乙酯溶液，同时，丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的pH值调整至8；The calcium lignosulfonate and ethyl acetate were mixed for the first time, the acrylic acid solution was mixed with 4-chloro-3,5-dimethylphenol for the second time, and then the calcium lignosulfonate and ethyl acetate were mixed for the second time. The mixed solution is filtered to obtain an ethyl acetate solution of calcium lignosulfonate, and at the same time, the pH value of the mixed solution of acrylic acid solution and 4-chloro-3,5-dimethylphenol is adjusted to 8;
准备甲醛溶液，预热至40℃，并使用氢氧化钠调节pH值至8，接着加入所有的尿素，充分搅拌，得到料液，然后开始升值至90℃，逐滴加入得到的木质素磺酸钙的乙酸乙酯溶液，搅拌混匀后并降温至60℃，接着逐滴加入得到的丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液，升温至95℃并搅拌均匀并加入氧化铝颗粒，最后降温至室温，出料。Prepare formaldehyde solution, preheat to 40°C, and use sodium hydroxide to adjust pH value to 8, then add all urea, stir well to get a feed liquid, then start to rise to 90°C, add the obtained lignosulfonic acid dropwise Calcium in ethyl acetate solution, stir and mix well and cool down to 60°C, then add dropwise the mixture of the obtained acrylic acid solution and 4-chloro-3,5-dimethylphenol, heat up to 95°C and stir evenly, Add alumina particles, finally cool down to room temperature, and discharge.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙与丙烯酸溶液的质量比为3：6，其中丙烯酸溶液的质量浓度为60％；The mass ratio of calcium lignosulfonate to acrylic acid solution is 3:6, and the mass concentration of acrylic acid solution is 60%;
乙酸乙酯的质量用量是木质素磺酸钙的2.5倍，4-氯-3,5-二甲基苯酚的质量用量是丙烯酸溶液的2倍；The mass dosage of ethyl acetate is 2.5 times that of calcium lignosulfonate, and the mass dosage of 4-chloro-3,5-dimethylphenol is 2 times that of acrylic acid solution;
其中4-氯-3,5-二甲基苯酚的质量浓度为99.0％。The mass concentration of 4-chloro-3,5-dimethylphenol was 99.0%.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
第一次混合的温度与第二次混合的温度均为90℃。The temperature of the first mixing and the temperature of the second mixing were both 90°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的存储温度为65℃，采用水浴方式；The storage temperature of the ethyl acetate solution of calcium lignosulfonate is 65°C, and the water bath mode is adopted;
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的温度控制在80℃。The temperature of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol was controlled at 80°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
所述的甲醛溶液的质量浓度为35％；The mass concentration of described formaldehyde solution is 35%;
所述的甲醛溶液与尿素之间的质量比为1：0.6。The mass ratio between the formaldehyde solution and the urea is 1:0.6.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
充分搅拌的转速为2000rpm。The rotational speed of thorough stirring was 2000 rpm.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的加入质量为料液的15％，The added mass of the ethyl acetate solution of calcium lignosulfonate is 15% of the feed liquid,
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的加入量为料液的8％。The added amount of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol is 8% of the feed solution.
3、有益效果3. Beneficial effects
相比于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
采用FT-IR对改性后的树脂进行表征分析，样品在1470cm-1-1680cm-1处具有苯环骨架特征吸收峰，说明4-氯-3,5-二甲基苯酚参与了树脂材料的分子链的形成；同时，磺酸基的特征峰(伸缩振动峰)并非发现，说明木质素磺酸钙并未参与上述分子链的形成，不存在接枝等，推测木质素磺酸钙起到物理共混作用。经推理，丙烯酸溶液可以起到促使形成二聚体、三聚体，促进交联密度加深，同时，木质素磺酸钙等的加入可能促使了树脂材料内部的缩聚，提高各项综合能力。The modified resin was characterized and analyzed by FT-IR, and the sample had characteristic absorption peaks of benzene ring skeleton at 1470cm -1 -1680cm -1 , indicating that 4-chloro-3,5-dimethylphenol was involved in the resin material. At the same time, the characteristic peak of sulfonic acid group (stretching vibration peak) is not found, indicating that calcium lignosulfonate does not participate in the formation of the above molecular chain, and there is no grafting, etc., it is speculated that calcium lignosulfonate plays a role in Physical blending. After reasoning, the acrylic acid solution can promote the formation of dimers and trimers, and promote the deepening of the cross-linking density. At the same time, the addition of calcium lignosulfonate may promote the polycondensation inside the resin material and improve various comprehensive capabilities.
附图说明Description of drawings
图1为本发明实施例1的产品的FT-IR图谱。Fig. 1 is the FT-IR spectrum of the product of Example 1 of the present invention.
具体实施方式Detailed ways
下面结合具体实施例对本发明进一步进行描述。The present invention will be further described below with reference to specific embodiments.
需要提醒的是，本申请涉及的试剂，均采购自上海阿拉丁生化科技股份有限公司。It should be reminded that the reagents involved in this application were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.
实施例1Example 1
共混改性树脂胶粘剂的制备方法，包括以下的操作步骤：The preparation method of the blended modified resin adhesive comprises the following operation steps:
准备木质素磺酸钙与丙烯酸溶液；Prepare calcium lignosulfonate and acrylic acid solution;
将木质素磺酸钙与乙酸乙酯第一次混合，并将丙烯酸溶液与4-氯-3,5-二甲基苯酚进行第二次混合，接着，木质素磺酸钙与乙酸乙酯的混合液进行过滤，获取木质素磺酸钙的乙酸乙酯溶液，同时，丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的pH值调整至8；The calcium lignosulfonate and ethyl acetate were mixed for the first time, the acrylic acid solution was mixed with 4-chloro-3,5-dimethylphenol for the second time, and then the calcium lignosulfonate and ethyl acetate were mixed for the second time. The mixed solution is filtered to obtain an ethyl acetate solution of calcium lignosulfonate, and at the same time, the pH value of the mixed solution of acrylic acid solution and 4-chloro-3,5-dimethylphenol is adjusted to 8;
准备甲醛溶液，预热至40℃，并使用氢氧化钠调节pH值至8，接着加入所有的尿素，充分搅拌，得到料液，然后开始升值至90℃，逐滴加入得到的木质素磺酸钙的乙酸乙酯溶液，搅拌混匀后并降温至60℃，接着逐滴加入得到的丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液，升温至95℃并搅拌均匀并加入氧化铝颗粒，最后降温至室温，出料。需要说明的是，氧化铝颗粒的添加质量百分比为其他物质的15％。Prepare formaldehyde solution, preheat to 40°C, and use sodium hydroxide to adjust pH value to 8, then add all urea, stir well to get a feed liquid, then start to rise to 90°C, add the obtained lignosulfonic acid dropwise Calcium in ethyl acetate solution, stir and mix well and cool down to 60°C, then add dropwise the mixture of the obtained acrylic acid solution and 4-chloro-3,5-dimethylphenol, heat up to 95°C and stir evenly, Add alumina particles, finally cool down to room temperature, and discharge. It should be noted that the added mass percentage of alumina particles is 15% of the other substances.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙与丙烯酸溶液的质量比为3：6，其中丙烯酸溶液的质量浓度为60％；The mass ratio of calcium lignosulfonate to acrylic acid solution is 3:6, and the mass concentration of acrylic acid solution is 60%;
乙酸乙酯的质量用量是木质素磺酸钙的2.5倍，4-氯-3,5-二甲基苯酚的质量用量是丙烯酸溶液的2倍；The mass dosage of ethyl acetate is 2.5 times that of calcium lignosulfonate, and the mass dosage of 4-chloro-3,5-dimethylphenol is 2 times that of acrylic acid solution;
其中4-氯-3,5-二甲基苯酚的质量浓度为99.0％。The mass concentration of 4-chloro-3,5-dimethylphenol was 99.0%.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
第一次混合的温度与第二次混合的温度均为90℃。The temperature of the first mixing and the temperature of the second mixing were both 90°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的存储温度为65℃，采用水浴方式；The storage temperature of the ethyl acetate solution of calcium lignosulfonate is 65°C, and the water bath mode is adopted;
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的温度控制在80℃。The temperature of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol was controlled at 80°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
所述的甲醛溶液的质量浓度为35％；The mass concentration of described formaldehyde solution is 35%;
所述的甲醛溶液与尿素之间的质量比为1：0.6。The mass ratio between the formaldehyde solution and the urea is 1:0.6.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
充分搅拌的转速为2000rpm。The rotational speed of thorough stirring was 2000 rpm.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的加入质量为料液的15％，The added mass of the ethyl acetate solution of calcium lignosulfonate is 15% of the feed liquid,
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的加入量为料液的8％。The added amount of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol is 8% of the feed solution.
需要提醒的是，上述操作需要考虑通风安全性，避免对身体造成有害影响。It should be reminded that the above operations need to consider ventilation safety to avoid harmful effects on the body.
对比方案1
共混改性树脂胶粘剂的制备方法，包括以下的操作步骤：The preparation method of the blended modified resin adhesive comprises the following operation steps:
准备十二烷基苯磺酸钙与丙烯酸溶液；Prepare calcium dodecylbenzenesulfonate and acrylic acid solution;
将十二烷基苯磺酸钙与乙酸乙酯第一次混合，并将丙烯酸溶液与4-氯-3,5-二甲基苯酚进行第二次混合，接着，十二烷基苯磺酸钙与乙酸乙酯的混合液进行过滤，获取十二烷基苯磺酸钙的乙酸乙酯溶液，同时，丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的pH值调整至8；A first mixing of calcium dodecylbenzenesulfonate with ethyl acetate and a second mixing of the acrylic acid solution with 4-chloro-3,5-dimethylphenol followed by dodecylbenzenesulfonic acid The mixed solution of calcium and ethyl acetate was filtered to obtain the ethyl acetate solution of calcium dodecylbenzenesulfonate, and at the same time, the pH value of the mixed solution of acrylic acid solution and 4-chloro-3,5-dimethylphenol was adjusted to 8;
准备甲醛溶液，预热至40℃，并使用氢氧化钠调节pH值至8，接着加入所有的尿素，充分搅拌，得到料液，然后开始升值至90℃，逐滴加入得到的十二烷基苯磺酸钙的乙酸乙酯溶液，搅拌混匀后并降温至60℃，接着逐滴加入得到的丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液，升温至95℃并搅拌均匀并加入氧化铝颗粒，最后降温至室温，出料。Prepare the formaldehyde solution, preheat to 40°C, and adjust the pH to 8 with sodium hydroxide, then add all the urea, stir well to obtain a feed liquid, then start to rise to 90°C, add the obtained dodecyl dropwise The ethyl acetate solution of calcium benzenesulfonate was stirred and mixed, and then cooled to 60 °C, then the mixture of the obtained acrylic acid solution and 4-chloro-3,5-dimethylphenol was added dropwise, and the temperature was raised to 95 °C and then cooled to 60 °C. Stir evenly, add alumina particles, and finally cool down to room temperature and discharge.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
十二烷基苯磺酸钙与丙烯酸溶液的质量比为3：6，其中丙烯酸溶液的质量浓度为60％；The mass ratio of calcium dodecylbenzenesulfonate to acrylic acid solution is 3:6, and the mass concentration of acrylic acid solution is 60%;
乙酸乙酯的质量用量是十二烷基苯磺酸钙的2.5倍，4-氯-3,5-二甲基苯酚的质量用量是丙烯酸溶液的2倍；The mass consumption of ethyl acetate is 2.5 times that of calcium dodecylbenzenesulfonate, and the mass consumption of 4-chloro-3,5-dimethylphenol is 2 times that of acrylic acid solution;
其中4-氯-3,5-二甲基苯酚的质量浓度为99.0％。The mass concentration of 4-chloro-3,5-dimethylphenol was 99.0%.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
第一次混合的温度与第二次混合的温度均为90℃。The temperature of the first mixing and the temperature of the second mixing were both 90°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
十二烷基苯磺酸钙的乙酸乙酯溶液的存储温度为65℃，采用水浴方式；The storage temperature of the ethyl acetate solution of calcium dodecylbenzenesulfonate is 65 ℃, and the water bath mode is adopted;
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的温度控制在80℃。The temperature of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol was controlled at 80°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
所述的甲醛溶液的质量浓度为35％；The mass concentration of described formaldehyde solution is 35%;
所述的甲醛溶液与尿素之间的质量比为1：0.6。The mass ratio between the formaldehyde solution and the urea is 1:0.6.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
充分搅拌的转速为2000rpm。The rotational speed of thorough stirring was 2000 rpm.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
十二烷基苯磺酸钙的乙酸乙酯溶液的加入质量为料液的15％，The added quality of the ethyl acetate solution of calcium dodecylbenzenesulfonate is 15% of the feed liquid,
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的加入量为料液的8％。The added amount of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol is 8% of the feed solution.
木质素磺酸钙改成十二烷基苯磺酸钙Calcium lignosulfonate changed to calcium dodecylbenzenesulfonate
对比方案2
共混改性树脂胶粘剂的制备方法，包括以下的操作步骤：The preparation method of the blended modified resin adhesive comprises the following operation steps:
准备木质素磺酸钙与丙烯酸溶液；Prepare calcium lignosulfonate and acrylic acid solution;
将木质素磺酸钙与乙酸乙酯第一次混合，并将丙烯酸溶液与苯酚进行第二次混合，接着，木质素磺酸钙与乙酸乙酯的混合液进行过滤，获取木质素磺酸钙的乙酸乙酯溶液，同时，丙烯酸溶液与苯酚的混合液的pH值调整至8；The calcium lignosulfonate and ethyl acetate are mixed for the first time, and the acrylic acid solution is mixed with phenol for the second time. Then, the mixed solution of calcium lignosulfonate and ethyl acetate is filtered to obtain calcium lignosulfonate At the same time, the pH value of the mixture of acrylic acid solution and phenol was adjusted to 8;
准备甲醛溶液，预热至40℃，并使用氢氧化钠调节pH值至8，接着加入所有的尿素，充分搅拌，得到料液，然后开始升值至90℃，逐滴加入得到的木质素磺酸钙的乙酸乙酯溶液，搅拌混匀后并降温至60℃，接着逐滴加入得到的丙烯酸溶液与苯酚的混合液，升温至95℃并搅拌均匀并加入氧化铝颗粒，最后降温至室温，出料。Prepare formaldehyde solution, preheat to 40°C, and use sodium hydroxide to adjust pH value to 8, then add all urea, stir well to get a feed liquid, then start to rise to 90°C, add the obtained lignosulfonic acid dropwise Calcium in ethyl acetate solution, after stirring and mixing, the temperature was lowered to 60 ° C, then the obtained mixture of acrylic acid solution and phenol was added dropwise, the temperature was raised to 95 ° C, stirred evenly, and alumina particles were added, and finally the temperature was lowered to room temperature. material.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙与丙烯酸溶液的质量比为3：6，其中丙烯酸溶液的质量浓度为60％；The mass ratio of calcium lignosulfonate to acrylic acid solution is 3:6, and the mass concentration of acrylic acid solution is 60%;
乙酸乙酯的质量用量是木质素磺酸钙的2.5倍，苯酚的质量用量是丙烯酸溶液的2倍；The mass dosage of ethyl acetate is 2.5 times that of calcium lignosulfonate, and the mass dosage of phenol is 2 times that of acrylic acid solution;
其中苯酚的质量浓度为99.0％。The mass concentration of phenol is 99.0%.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
第一次混合的温度与第二次混合的温度均为90℃。The temperature of the first mixing and the temperature of the second mixing were both 90°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的存储温度为65℃，采用水浴方式；The storage temperature of the ethyl acetate solution of calcium lignosulfonate is 65°C, and the water bath mode is adopted;
丙烯酸溶液与苯酚的混合液的温度控制在80℃。The temperature of the mixed solution of acrylic acid solution and phenol was controlled at 80°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
所述的甲醛溶液的质量浓度为35％；The mass concentration of described formaldehyde solution is 35%;
所述的甲醛溶液与尿素之间的质量比为1：0.6。The mass ratio between the formaldehyde solution and the urea is 1:0.6.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
充分搅拌的转速为2000rpm。The rotational speed of thorough stirring was 2000 rpm.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的加入质量为料液的15％，The added mass of the ethyl acetate solution of calcium lignosulfonate is 15% of the feed liquid,
丙烯酸溶液与苯酚的混合液的加入量为料液的8％。The added amount of the mixed solution of acrylic acid solution and phenol is 8% of the feed solution.
对比方案3Contrast plan 3
共混改性树脂胶粘剂的制备方法，包括以下的操作步骤：The preparation method of the blended modified resin adhesive comprises the following operation steps:
准备木质素磺酸钙与丙烯酸溶液；Prepare calcium lignosulfonate and acrylic acid solution;
将木质素磺酸钙与乙酸乙酯第一次混合，并将丙烯酸溶液与4-氯-3,5-二甲基苯酚进行第二次混合，接着，木质素磺酸钙与乙酸乙酯的混合液进行过滤，获取木质素磺酸钙的乙酸乙酯溶液，同时，丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的pH值调整至8；The calcium lignosulfonate and ethyl acetate were mixed for the first time, the acrylic acid solution was mixed with 4-chloro-3,5-dimethylphenol for the second time, and then the calcium lignosulfonate and ethyl acetate were mixed for the second time. The mixed solution is filtered to obtain an ethyl acetate solution of calcium lignosulfonate, and at the same time, the pH value of the mixed solution of acrylic acid solution and 4-chloro-3,5-dimethylphenol is adjusted to 8;
将得到的木质素磺酸钙的乙酸乙酯溶液，加入到丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液，升温至95℃并搅拌均匀并加入氧化铝颗粒，最后降温至室温，出料。The obtained ethyl acetate solution of calcium lignosulfonate was added to the mixed solution of acrylic acid solution and 4-chloro-3,5-dimethylphenol, the temperature was raised to 95°C and stirred evenly, and alumina particles were added, and finally the temperature was lowered. To room temperature, discharge.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙与丙烯酸溶液的质量比为3：6，其中丙烯酸溶液的质量浓度为60％；The mass ratio of calcium lignosulfonate to acrylic acid solution is 3:6, and the mass concentration of acrylic acid solution is 60%;
乙酸乙酯的质量用量是木质素磺酸钙的2.5倍，4-氯-3,5-二甲基苯酚的质量用量是丙烯酸溶液的2倍；The mass dosage of ethyl acetate is 2.5 times that of calcium lignosulfonate, and the mass dosage of 4-chloro-3,5-dimethylphenol is 2 times that of acrylic acid solution;
其中4-氯-3,5-二甲基苯酚的质量浓度为99.0％。The mass concentration of 4-chloro-3,5-dimethylphenol was 99.0%.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
第一次混合的温度与第二次混合的温度均为90℃。The temperature of the first mixing and the temperature of the second mixing were both 90°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的存储温度为65℃，采用水浴方式；The storage temperature of the ethyl acetate solution of calcium lignosulfonate is 65°C, and the water bath mode is adopted;
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的温度控制在80℃。The temperature of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol was controlled at 80°C.
上述所述的改性树脂胶粘剂的制备方法中，In the preparation method of the above-mentioned modified resin adhesive,
木质素磺酸钙的乙酸乙酯溶液的加入质量为料液的15％，The added mass of the ethyl acetate solution of calcium lignosulfonate is 15% of the feed liquid,
丙烯酸溶液与4-氯-3,5-二甲基苯酚的混合液的加入量为料液的8％。The added amount of the mixed solution of the acrylic acid solution and 4-chloro-3,5-dimethylphenol is 8% of the feed solution.
实施例2Example 2
采用FT-IR对改性后的树脂(实施例1制备的样品，KBr涂膜制样法)进行表征分析，如图1所示(委托本地的高校实验室进行测试)，其中图1中上图为酚醛树脂的标准谱图，其中图1中下图为共混改性后的树脂样品的谱图，样品在1470cm-1-1680cm-1处具有苯环骨架特征吸收峰，说明4-氯-3,5-二甲基苯酚参与了树脂材料的分子链的形成；同时，磺酸基的特征峰(伸缩振动峰)并非发现，说明木质素磺酸钙并未参与上述分子链的形成，不存在接枝等，推测木质素磺酸钙起到物理共混作用。The modified resin (sample prepared in Example 1, KBr coating sample preparation method) was characterized and analyzed by FT-IR, as shown in Figure 1 (entrusted to a local university laboratory for testing), in which the upper part of Figure 1 The picture shows the standard spectrum of phenolic resin. The bottom picture in Figure 1 is the spectrum of the resin sample after blending and modification. The sample has a characteristic absorption peak of benzene ring skeleton at 1470cm -1 -1680cm -1 , indicating that 4-chlorine -3,5-dimethylphenol participated in the formation of the molecular chain of the resin material; at the same time, the characteristic peak (stretching vibration peak) of the sulfonic acid group was not found, indicating that calcium lignosulfonate did not participate in the formation of the above-mentioned molecular chain, There is no grafting, etc., it is presumed that calcium lignosulfonate plays a role of physical blending.
实施例3Example 3
选择实施例1、对比方案1、对比方案2及对比方案3，进行如下测试：Select Example 1,
(1)黏度：(1) Viscosity:
采用涂-4杯黏度计进行测定，以树脂从小孔流出到流柱中断所需时间作为衡量指标。The measurement was carried out with a Tu-4 cup viscometer, and the time required for the resin to flow from the small hole to the interruption of the flow column was used as a measure.
(2)胶接强度：(2) Bonding strength:
按照GB/T 14074—2006标准，采用电子万能试验机进行测定(拉伸速率6000N/min，25℃测定)。According to GB/T 14074-2006 standard, it was measured by electronic universal testing machine (tensile rate 6000N/min, measured at 25℃).
(3)阻燃性能(氧指数)(3) Flame retardant properties (oxygen index)
按GB/T 2406—2009测试材料的氧指数(LOI)。The oxygen index (LOI) of the material is tested according to GB/T 2406-2009.
表1测试结果Table 1 Test results
如表1所示，本申请制备的产品，其黏度高达98.7s，且胶接强度为7.35MPa，同时具有较高的阻燃性能，可见综合性能优良。As shown in Table 1, the product prepared in this application has a viscosity as high as 98.7s, and a bonding strength of 7.35MPa, and at the same time has high flame retardant performance, showing excellent comprehensive performance.
以上内容是结合具体实施方式对本发明作进一步详细说明，不能认定本发明具体实施只局限于这些说明，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明的构思的前提下，还可以做出若干简单的推演或替换，都应当视为属于本发明所提交的权利要求书确定的保护范围。The above content is to further describe the present invention in conjunction with the specific embodiments, and it cannot be considered that the specific implementation of the present invention is limited to these descriptions. Several simple deductions or substitutions can also be made, all of which should be regarded as belonging to the protection scope determined by the claims submitted in the present invention.
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| US3077458A (en) * | 1957-05-27 | 1963-02-12 | Alim Corp | Non-aqueous fire ret ardant composition comprising a urea formaldehyde condensate |
| CA2711182A1 (en) * | 2008-01-04 | 2009-07-16 | Guang Yang | A new lumber adhesive and the preparation thereof |
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| CN111087956A (en) * | 2019-12-09 | 2020-05-01 | 华南农业大学 | Modified phenolic resin adhesive and preparation method and application thereof |
| CN112625627A (en) * | 2020-12-11 | 2021-04-09 | 中南林业科技大学 | Preparation method of lignin modified environment-friendly urea-formaldehyde resin adhesive |
| CN113249070A (en) * | 2021-05-13 | 2021-08-13 | 广西国旭春天人造板有限公司 | Urea-formaldehyde resin adhesive suitable for glue spraying assembly process and preparation method thereof |
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| US3077458A (en) * | 1957-05-27 | 1963-02-12 | Alim Corp | Non-aqueous fire ret ardant composition comprising a urea formaldehyde condensate |
| CA2711182A1 (en) * | 2008-01-04 | 2009-07-16 | Guang Yang | A new lumber adhesive and the preparation thereof |
| CN105666632A (en) * | 2016-01-25 | 2016-06-15 | 新沂市大自然木业有限公司 | Manufacturing method for environment-friendly corrosion prevention medium-density fiberboard for door plate of security door |
| CN111087956A (en) * | 2019-12-09 | 2020-05-01 | 华南农业大学 | Modified phenolic resin adhesive and preparation method and application thereof |
| CN112625627A (en) * | 2020-12-11 | 2021-04-09 | 中南林业科技大学 | Preparation method of lignin modified environment-friendly urea-formaldehyde resin adhesive |
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Denomination of invention: Preparation method of a blend modified resin adhesive Granted publication date: 20240709 Pledgee: China Construction Bank Corporation Guangyuan Branch Pledgor: GUANGYUAN RUIFENG NEW MATERIALS Co.,Ltd. Registration number: Y2024980053042 |