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CN-121991630-A - Plasticizer corrosion resistant yellow adhesive and preparation method thereof

CN121991630ACN 121991630 ACN121991630 ACN 121991630ACN-121991630-A

Abstract

The invention provides a plasticizer corrosion resistant yellow adhesive and a preparation method thereof, wherein the yellow adhesive comprises, by weight, 10-14 parts of 1, 4-butanediol adipic acid polyester polyol, 4-8 parts of polycaprolactone polyol, 1-3 parts of diphenylmethane diisocyanate, 0.05-0.15 part of 1, 6-hexanediol, 1-2 parts of hydroxyethyl methacrylate, 0.01-0.03 part of an organobismuth catalyst and 75-80 parts of butanone. According to the invention, through the cooperation of polycaprolactone polyol and polyester polyol, the polyurethane prepolymer with specific crystallization performance is synthesized, and the yellow gum is endowed with excellent plasticizer corrosion resistance and low-temperature activation capability. The active groups in the polyurethane prepolymer are grafted and copolymerized with neoprene and MMA, and a plasticizer-resistant polyurethane chain segment is introduced on a neoprene molecular chain to form a hard segment-soft segment alternating block structure, and the corrosion resistance and the viscoelasticity are both considered.

Inventors

  • Xu tongzhou
  • ZHENG LIHUA
  • LIANG JIANFENG

Assignees

  • 广东多正树脂科技有限公司

Dates

Publication Date
20260508
Application Date
20260311

Claims (8)

  1. 1. The plasticizer corrosion resistant yellow adhesive is characterized by comprising, by weight, 20-40 parts of polyurethane prepolymer, 10-16 parts of neoprene sheet, 6-10 parts of methyl methacrylate, 0.1-0.3 part of benzoyl peroxide, 0.1-0.3 part of an anti-aging agent, 4-8 parts of butanone, 15-35 parts of cyclohexane, 6-10 parts of dimethyl carbonate and 5-12 parts of tackifying resin, wherein the polyurethane prepolymer comprises, by weight, 10-14 parts of 1, 4-butanediol adipic acid polyester polyol, 4-8 parts of polycaprolactone polyol, 1-3 parts of diphenylmethane diisocyanate, 0.05-0.15 part of 1, 6-hexanediol, 1-2 parts of hydroxyethyl methacrylate, 0.01-0.03 part of an organic bismuth catalyst and 75-80 parts of butanone.
  2. 2. The plasticizer corrosion resistant yellow gum according to claim 1, wherein the tackifying resin is compounded from terpene-phenol resin, rosin-modified resin and phenolic resin.
  3. 3. The plasticizer corrosion resistant yellow gel according to claim 1, wherein the tackifying resin comprises, by weight, 3-6 parts of terpene-phenol resin, 1-3 parts of rosin-modified resin and 3-5 parts of phenolic resin.
  4. 4. A plasticizer corrosion resistant yellow gel according to claim 1, wherein the weight ratio of 1, 4-butanediol adipate polyester polyol to polycaprolactone polyol in the polyurethane prepolymer is (1.5-3): 1.
  5. 5. The plasticizer corrosion resistant yellow gum of claim 1, wherein the polycaprolactone polyol has a molecular weight of 2000-4000.
  6. 6. The plasticizer corrosion resistant yellow gel of claim 1, wherein said neoprene sheet is a chloroprene rubber sheet.
  7. 7. The plasticizer corrosion resistant yellow gum of claim 1, wherein the anti-aging agent is 2, 6-di-t-butyl-p-cresol.
  8. 8. A process for preparing the plasticizer corrosion resistant yellow gum according to any one of claims 1-7 includes such steps as synthesizing polyurethane prepolymer, adding 1, 4-butanediol adipic acid polyester polyol and polycaprolactone polyol into vacuum prepolymer reactor, heating to 110-130 deg.C, vacuum dewatering for 0.5-1 hr, cooling to 85-95 deg.C, adding 30% of butanone, stirring, adding organic Bi catalyst, 3) controlling the temp at 80-85 deg.C, dropping diphenyl methane diisocyanate, stirring for 10-20min, adding 1, 6-hexanediol, stirring, monitoring the current value of reaction system, increasing molecular weight to 75-85A, adding butanone 15% and hydroxy ethyl methacrylate, reacting at 75-85 deg.C for 0.5-1.5 hr, adding methyl butanone to 5-5 deg.C, stirring to obtain the final product, adding methyl butanone 1-5 deg.C, stirring to obtain the final product, adding methyl butanone, stirring to obtain the final product, stirring until the final product is prepared by stirring until the final product is prepared, adding methyl butanone 1-5-methyl ketone to obtain the final product, stirring until the final product is prepared by stirring until the final product is 75-85 deg.C, and the final product is prepared by stirring until the final product is 75-85 deg.C, maintaining the temperature of 80-85 ℃ for 2-4h, monitoring the current value to 65-75A, indicating that the grafting reaction reaches the target degree, cooling to 60-70 ℃, adding dimethyl carbonate and an anti-aging agent, stirring for 20-40min, blending the tackifying resin, namely (1) continuously adding the tackifying resin, stirring at a high speed for 1-2h until the tackifying resin is completely dissolved, sampling and testing the viscosity, ensuring the viscosity to be 4000-5000cps/25 ℃, regulating the viscosity to 4000-5000cps/25 ℃ by using dimethyl carbonate when the viscosity is higher than 5000cps/25 ℃, filtering and discharging, and obtaining the plasticizer corrosion resistant yellow adhesive finished product.

Description

Plasticizer corrosion resistant yellow adhesive and preparation method thereof Technical Field The invention relates to the technical field of PVC adhesives, in particular to a plasticizer corrosion resistant yellow adhesive and a preparation method thereof, which are particularly suitable for normal-temperature adhesion of PVC artificial leather, PVC films, EVA, rubber and other base materials. Background PVC (polyvinyl chloride) materials are widely applied to the fields of shoe materials, bags, furniture, automobile interiors and the like due to the characteristics of high quality, low cost, good weather resistance, easy processing and forming and the like. In these applications, it is often necessary to attach the PVC material to other substrates (e.g., EVA, rubber, fabric, etc.) via an adhesive. However, PVC articles generally contain 20-50wt% of plasticizers (e.g., phthalates) for flexibility. The plasticizers gradually migrate and separate out to the adhesive layer in the use process, and the traditional chloroprene rubber adhesive has swelling and dissolving effects, so that the adhesive film is softened, the cohesive strength is reduced, and finally the adhesive force is quickly attenuated and even completely degummed. Experiments show that the peel strength of traditional neoprene bonded PVC articles typically drops by more than 50% after 7 days at 50 ℃ and substantially loses adhesion after 30 days. The polyurethane adhesive has better resistance to plasticizers because of the higher-polarity carbamate groups in the molecular structure, and is the mainstream choice for bonding PVC materials in industry at present. However, the polyurethane adhesive has obvious defects that the activation temperature is generally above 50 ℃, an oven or heating equipment is required to be equipped, the operation energy consumption is high, the efficiency is low, and the heating activation is difficult to implement for large or irregular workpieces, so that the production efficiency and the application range are severely restricted. Aiming at the problems, chinese patent application No. CN202110308832.X discloses a yellow adhesive for resisting plasticizer migration and a preparation method thereof, wherein EVM (ethylene-vinyl acetate copolymer) rubber is adopted for modifying neoprene. However, the EVM rubber as a core raw material of the technology is mainly imported at present, the capacity of stable quantity is not yet available in China, quality fluctuation among imported raw material batches is large, the quality of a product is unstable, and the requirement of large-scale industrial production is difficult to meet. In addition, the compatibility of EVM rubber and neoprene is limited, and the excessive addition amount can lead to the separation of colloid phase, and the adhesive property is affected. Therefore, there is a need in the art to develop a novel yellow adhesive with stable raw material source, normal temperature operation, excellent plasticizer corrosion resistance and durable adhesion, so as to replace the existing import dependent technology and meet the urgent demands of the PVC product industry. Disclosure of Invention Aiming at the problems of plasticizer corrosion resistance yellow glue in the prior art, the invention provides plasticizer corrosion resistance yellow glue and a preparation method thereof, domestic raw materials are adopted, effective bonding can be realized within a wide temperature range of 10-70 ℃, and bonding strength of a bonded material at a breaking level can be maintained after accelerated aging for 30 days at 50 ℃, so that the triple technical problems that the plasticizer corrosion resistance of neoprene is not realized, polyurethane glue needs to be activated by heating and EVM modified raw materials depend on import in the prior art are fundamentally solved. The plasticizer corrosion resistant yellow adhesive comprises, by weight, 20-40 parts of a polyurethane prepolymer, 10-16 parts of a neoprene sheet, 6-10 parts of Methyl Methacrylate (MMA), 0.1-0.3 part of Benzoyl Peroxide (BPO), 0.1-0.3 part of an anti-aging agent, 4-8 parts of butanone, 15-35 parts of cyclohexane, 6-10 parts of dimethyl carbonate and 5-12 parts of tackifying resin, wherein the polyurethane prepolymer comprises, by weight, 10-14 parts of 1, 4-butanediol adipic acid polyester polyol, 4-8 parts of polycaprolactone polyol, 1-3 parts of diphenylmethane diisocyanate (MDI), 0.05-0.15 part of 1, 6-hexanediol, 1-2 parts of hydroxyethyl methacrylate, 0.01-0.03 part of an organic bismuth catalyst and 75-80 parts of butanone. The raw materials in the invention are domestic industrial grade commodities. According to the invention, through the synergistic use of polycaprolactone polyol and 1, 4-butanediol adipic acid polyester polyol, the polyurethane prepolymer with specific crystallization property is synthesized, and the yellow gum is endowed with excellent plasticizer corrosion resistance and low-tempera