WO2025251404A1 - Résine de polyester et procédé de préparation associé, adhésif polyester sensible à la pression et produit adhésif sensible à la pression - Google Patents

Résine de polyester et procédé de préparation associé, adhésif polyester sensible à la pression et produit adhésif sensible à la pression

Info

Publication number
WO2025251404A1
WO2025251404A1 PCT/CN2024/109570 CN2024109570W WO2025251404A1 WO 2025251404 A1 WO2025251404 A1 WO 2025251404A1 CN 2024109570 W CN2024109570 W CN 2024109570W WO 2025251404 A1 WO2025251404 A1 WO 2025251404A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
diol
carboxyl
sensitive adhesive
polyester resin
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.)
Pending
Application number
PCT/CN2024/109570
Other languages
English (en)
Chinese (zh)
Inventor
李璐
董万旭
陈文娟
苏嘉辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Jf Bio Products Co Ltd
Original Assignee
Shenzhen Jf Bio Products Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen Jf Bio Products Co Ltd filed Critical Shenzhen Jf Bio Products Co Ltd
Publication of WO2025251404A1 publication Critical patent/WO2025251404A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
    • C09J169/005—Polyester-carbonates
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2467/00—Presence of polyester
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2469/00—Presence of polycarbonate

Definitions

  • This application belongs to the field of pressure-sensitive adhesive technology, specifically, this application relates to polyester resin, its preparation method, polyester pressure-sensitive adhesive and pressure-sensitive adhesive products.
  • Pressure-sensitive adhesives are viscoelastic materials that possess both the viscous properties of liquids and the elastic properties of solids. Using finger pressure, the adhesive can immediately bond to any smooth surface, and if the bonding surface is damaged, the adhesive will not contaminate it. In recent years, with the increasing demand for packaging, office supplies, and various labels, the demand for pressure-sensitive adhesives has also been growing.
  • PSAs typically consist of three main components: a base resin, a tackifying resin, and a plasticizer.
  • the base resin enhances the cohesive strength of the PSA, while the tackifying resin provides initial tack.
  • the addition of tackifying resin to traditional PSA formulations, while imparting pressure sensitivity to the base resin significantly weakens its cohesive properties, resulting in a decrease in the overall peel strength and holding power of the PSA tape. This is because conventional base resins do not contain long-chain branches, and the base resin and tackifying resin often belong to different categories of resins with poor compatibility. This leads to significant phase separation in the PSA formulation, thus affecting the holding power of the PSA.
  • US Patent Application US20170283666A1 discloses a pressure-sensitive adhesive composition
  • a pressure-sensitive adhesive composition comprising a block copolymer, wherein the block copolymer comprises a first block having a glass transition temperature of 50°C or higher, and a second block having a glass transition temperature of -10°C or lower, wherein the first block may be an alkyl acrylate (meth)acrylate, and the second block may be an alkyl acrylate of an alkyl group having 1 to 4 carbon atoms.
  • this pressure-sensitive adhesive composition has the defects of poor tack and low peel strength.
  • Biodegradable hot melt pressure-sensitive adhesive comprising the following components by weight: 65-85 parts biodegradable plastic, 5-25 parts biodegradable tackifying resin, 1-9 parts biodegradable plasticizer, 0-10 parts filler, and 1 part antioxidant.
  • the biodegradable plastic is one or more of polybutylene succinate, polylactic acid, polyglycolic acid, polybutylene terephthalate-adipate, and polypropylene carbonate.
  • the biodegradable tackifying resin is one or more of rosin, hydrogenated rosin, disproportionated rosin, esterified rosin, C5 petroleum resin, C9 petroleum resin, and terpene resin.
  • this pressure-sensitive adhesive has poor adhesion and holding power.
  • Biodegradable thermoplastic elastomer which is composed of the following components: 20-120 parts of biodegradable resin, 10-120 parts of filler, 0.2-5 parts of coupling agent, 0.03-5 parts of crosslinking agent, 0.1-10 parts of co-crosslinking agent, 0.2-10 parts of slip agent, 5-100 parts of plasticizer, and 0.1-40 parts of solvent.
  • the biodegradable resin is one or more of polybutylene succinate, polybutylene adipate, polybutylene adipate terephthalate, polylactic acid, polypropylene carbonate, polycaprolactone, polyhydroxyalkanoate, and polyvinyl alcohol. The tack and adhesion of this elastomer cannot meet the requirements of pressure-sensitive adhesives.
  • Cisoka patent application CN117384577A discloses a carbon dioxide-based biodegradable pressure-sensitive adhesive material.
  • Diacetyl-L-tartaric anhydride is added to the polymerization reaction of carbon dioxide and epoxide, and the carbon dioxide-based biodegradable pressure-sensitive adhesive material is prepared by ternary polymerization.
  • the carbon dioxide-based biodegradable pressure-sensitive adhesive material is prepared by ternary polymerization.
  • it when used as a pressure-sensitive adhesive resin to prepare pressure-sensitive adhesives, it has poor compatibility with tackifying resins, obvious phase separation, and the adhesion and holding power of the pressure-sensitive adhesive cannot meet the requirements.
  • the present application aims to overcome at least one defect of the prior art and provide a polyester resin, a preparation method, and a polyester pressure-sensitive adhesive.
  • this application relates to a polyester-type resin, wherein the polyester-type resin is a copolymer of a carboxyl-terminated polyester, a non-crystalline carbon dioxide-based polyester diol, and a modified diol, wherein the mass ratio of the carboxyl-terminated polyester, the non-crystalline carbon dioxide-based polyester diol, and the modified diol is (10 ⁇ 30):(50 ⁇ 99):(2 ⁇ 30), and the structural formula of the modified diol is shown in Formula 1, Formula 2, or Formula 3.
  • the polyester-type resin is a copolymer of a carboxyl-terminated polyester, a non-crystalline carbon dioxide-based polyester diol, and a modified diol, wherein the mass ratio of the carboxyl-terminated polyester, the non-crystalline carbon dioxide-based polyester diol, and the modified diol is (10 ⁇ 30):(50 ⁇ 99):(2 ⁇ 30), and the structural formula of the modified diol is shown in Formula 1, Formula 2, or Formula 3.
  • R1 is a C1-12 alkyl group
  • R2 is a C1-12 alkyl group
  • R3 is a C1-12 alkyl group
  • R4 is H or a C1-12 alkyl group
  • R5 is a C1-12 alkyl group.
  • this application relates to a method for preparing a polyester resin, comprising the following steps:
  • the carboxyl-terminated polyester, the amorphous carbon dioxide-based polyester diol, and the modified diol are added to a reactor in the following mass ratios: (10 ⁇ 30):(50 ⁇ 99):(2 ⁇ 30). After heating to 100 ⁇ 180°C, a catalyst of 1 ⁇ 2% of the total mass of the carboxyl-terminated polyester, the amorphous carbon dioxide-based polyester diol, and the modified diol is added. Vacuum polycondensation is then performed, followed by cooling to obtain the polyester resin.
  • this application also relates to a polyester-type pressure-sensitive adhesive, comprising the following components in parts by weight: 50 to 99 parts of the polyester-type resin and 0.1 to 10 parts of additives.
  • this application also relates to a pressure-sensitive adhesive product, including a substrate and a pressure-sensitive adhesive layer attached to the substrate, wherein the pressure-sensitive adhesive layer includes the polyester-type pressure-sensitive adhesive.
  • the beneficial effects of this application are as follows: the polyester resin described in this application has excellent properties, and the peel strength and bonding performance of the polyester pressure-sensitive adhesive prepared from it are superior to those of existing pressure-sensitive adhesives.
  • Figure 1 shows the infrared spectrum of modified diol 1.
  • the polyester resin includes the modified diol of Formula 1, Formula 2 or Formula 3, which has side chains containing ester groups.
  • the modified diol and amorphous carbon dioxide-based polyester diol and carboxyl-terminated polyester are reacted in a certain proportion to prepare a polyester resin containing carboxyl-terminated polyester segments, amorphous carbon dioxide-based polyester segments and side chain segments.
  • the carboxyl-terminated polyester segments are hard segments that can be used to ensure the cohesive strength of the polyester resin.
  • the amorphous carbon dioxide-based polyester segments are soft segments that can ensure the elasticity of the polyester resin.
  • the modified diol segments contain side chains that are incorporated into the polyester resin, thereby increasing the branching degree of the polyester resin, lowering the glass transition temperature, and enhancing the overall molecular chain mobility of the resin.
  • the ester groups contained in the side chains can provide a large number of hydrogen bonds, which easily form hydrogen bond adhesion with the adhesive substrate, resulting in good initial tack.
  • R1 can be an alkyl group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12, and R1 is preferably an alkyl group of C1-4.
  • R2 can be an alkyl group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12, and R2 is preferably an alkyl group of C1-4.
  • R3 can be an alkyl group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12, and R3 is preferably an alkyl group of C1-4.
  • R4 can be H, or an alkyl group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12, and R4 is preferably an alkyl group of C1-4.
  • R5 can be an alkyl group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12, and R5 is preferably an alkyl group of C1-4.
  • the required mass fraction is 3 or more.
  • the mass fraction of the modified diol should be below 30.
  • the mass fraction of the modified diol is preferably 4 to 25, more preferably 5 to 20, and also 7, 9, 11, 13, 15, 17, or 19.
  • the number-average molecular weight of the carboxyl-terminated polyester can be between 1,000 and 3,000. Since the molecular weight of each segment affects the performance of the polyester resin, for the carboxyl-terminated polyester, the higher the molecular weight, the stronger the crystallinity and the stronger its ability to act as a physical crosslinking point. To obtain better performance, the number-average molecular weight of the carboxyl-terminated polyester can be above 1,000. However, excessively high molecular weight leads to increased crystallinity, resulting in greater microphase separation in the polyester pressure-sensitive adhesive, which in turn leads to a decrease in the performance of the polyester pressure-sensitive adhesive. Therefore, the number-average molecular weight of the carboxyl-terminated polyester can be below 3,000. Specifically, the number-average molecular weight of the carboxyl-terminated polyester can be 1,200, 1,400, 1,600, 1,800, 2,000, 2,200, 2,400, 2,600, 2,800, or 2,900.
  • the mass fraction of the carboxyl-terminated polyester is 10-30. Since the carboxyl-terminated polyester contains carboxyl groups, it can act as a physical crosslinking point to form a polyester-type resin with carbon dioxide-based polyester diol, thereby improving the overall cohesive strength of the resin and enabling it to meet the adhesive properties required for pressure-sensitive adhesives.
  • the mass fraction of the carboxyl-terminated polyester can be 10 parts or more. As its content increases, the cohesive properties of the polyester-type resin increase, but excessively high carboxyl-terminated polyester content leads to increased phase separation, resulting in decreased elastomer properties and consequently, decreased performance of the subsequent pressure-sensitive adhesive.
  • the mass fraction of the carboxyl-terminated polyester is controlled to be below 30 parts.
  • the mass fraction of the carboxyl-terminated polyester can be 12, 14, 16, 18, 20, 22, 24, 26, or 28.
  • the carboxyl-terminated polyester is polymerized from a C3-7 diacid and a C3-7 diol.
  • the carboxyl-terminated polyester is preferably polybutylene succinate (PBS).
  • PBS is a novel biodegradable polymer material. Its degradation mechanism involves first hydrolysis of the C-O bonds, followed by further degradation under enzymatic action.
  • PBS is a crystalline substance that can act as a physical crosslinking point to form a copolyester elastomer with polycarbonate, thereby improving the overall cohesive strength of the resin. This allows it to be used in pressure-sensitive adhesives, meeting the higher adhesion requirements of these adhesives.
  • PBS is synthesized from biomass, a second type of carbon source, and exhibits good degradation performance.
  • the carboxyl-terminated polybutylene succinate has a hydroxyl value of 37.4–112 mgKOH/g and a molecular weight of 1,000–3,000.
  • the number-average molecular weight of the amorphous carbon dioxide-based polyester diol is 2,000 to 4,000.
  • the amorphous carbon dioxide-based polyester diol segments if the molecular weight is too small, the segments are too short, and the elasticity of the polyester resin will decrease. Therefore, its number-average molecular weight is preferably above 2,000. Conversely, if the molecular weight is too large, it corresponds to a decrease in the content of the carboxyl-terminated polyester, resulting in a decrease in the strength of the polyester resin.
  • the number-average molecular weight is preferably controlled to be below 3,000. Specifically, the number-average molecular weight of the amorphous carbon dioxide-based polyester diol segments can be 2,200, 2,400, 2,600, 2,800, 3,000, 3,200, 3,400, 3,600, or 3,800.
  • the amorphous carbon dioxide-based polyester diol is preferably polypropylene carbonate diol (PPC), with a number-average molecular weight preferably between 2,000 and 4,000.
  • PPC is also a novel biodegradable polymer material, being a CO2- based diol derived from a third type of carbon source, exhibiting rapid degradation and a high degradation rate.
  • the hydroxyl value of the non-crystalline carbon dioxide-based polyester diol is 28.05 ⁇ 56.1 mgKOH/g.
  • the polyester resin has a molecular weight of 20,000 to 60,000, and the number average molecular weight is preferably 25,000 to 40,000, more preferably 28,000 to 38,000.
  • the number average molecular weight is preferably 25,000 to 40,000, more preferably 28,000 to 38,000.
  • a molecular weight of 20,000 or higher is preferred to obtain better cohesion. Excessive molecular weight can lead to a decrease in degradation performance; therefore, a number-average molecular weight of 60,000 or lower is preferred.
  • the number-average molecular weight of polyester resins can be 22,000, 24,000, 26,000, 28,000, 30,000, 32,000, 34,000, 36,000, 38,000, 40,000, 42,000, 44,000, 46,000, 48,000, 50,000, 52,000, 54,000, 56,000, or 58,000.
  • carboxyl-terminated polyesters can be made from new biodegradable polymers, and non-crystalline carbon dioxide-based polyester diols are novel biodegradable polymers, the prepared polyester resins have good biodegradability.
  • the modified diols and carboxyl-terminated polyesters and non-crystalline carbon dioxide-based polyester diols were reacted in a certain proportion to obtain a polyester-type resin.
  • This polyurethane pressure-sensitive adhesive resin contains carboxyl-terminated polyester segments, carbon dioxide-based polyester segments, and side chain segments.
  • the modified diol segments contain side chains, which are incorporated into the polyester resin, thereby increasing the branching degree of the polyester resin and enhancing the overall molecular chain activity of the resin.
  • the ester bonds contained in the side chains can provide a large number of hydrogen bonds, making it easy to form hydrogen bond adhesion with the adhesive substrate, resulting in good initial tack.
  • carboxyl-terminated polyester, non-crystalline carbon dioxide-based polyester diol, and the modified diol are added to a reaction vessel in a mass ratio of (10 ⁇ 20):(60 ⁇ 90):(5 ⁇ 20).
  • a catalyst of 3wt ⁇ 8wt ⁇ of the total mass of the carboxyl-terminated polyester, non-crystalline carbon dioxide-based polyester diol, and the modified diol is added.
  • vacuum polycondensation for 3 ⁇ 4 hours the mixture is cooled to room temperature to obtain polyester resin, wherein the vacuum degree is within 0.5 mmHg.
  • the preparation of the modified diol includes the following steps:
  • an alkanolamine compound is added to an organic solvent, and an acrylate compound is added dropwise under an inert gas protection.
  • the reaction is carried out at 15-35°C for 10-30 hours, followed by water washing and liquid-liquid extraction, and then vacuum distillation to remove the organic solvent to obtain the modified diol.
  • the molar ratio of the alkanolamine compound to the acrylate compound is preferably (1-1.2):1.
  • the inert gas is preferably nitrogen and/or argon.
  • the alkanolamine compound is one or more selected from diethanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-1,3-propanediol, and 3-amino-1,2-propanediol.
  • the acrylate compound is one or more of isooctyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, isooctyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
  • the organic solvent is methanol, ethanol, or dimethylformamide.
  • the catalyst is tetrabutyl titanate, tetraisopropyl titanate, or p-toluenesulfonic acid.
  • the polyester resin is preferably 60-99 parts, more preferably 80-99 parts, and may also be 90-99 parts, or 95-99 parts. Since the polyester resin itself readily forms hydrogen bonds with the adhesive substrate, exhibiting good initial tack, the tackifying resin is an optional component.
  • the polyester-based pressure-sensitive adhesive possesses good cohesive properties, and the peel strength and holding power of the pressure-sensitive adhesive can also be improved.
  • the polyester pressure-sensitive adhesive may further include 1 to 50 parts of tackifying resin, wherein the tackifying resin is one or more of natural rosin, hydrogenated rosin, disproportionated rosin, esterified rosin, C5 petroleum resin, C9 petroleum resin, and terpene resin.
  • the tackifying resin is one or more of natural rosin, hydrogenated rosin, disproportionated rosin, esterified rosin, C5 petroleum resin, C9 petroleum resin, and terpene resin.
  • the additives include plasticizers, antioxidants, fillers, pigments, rheology modifiers, elastomers, light stabilizers, ultraviolet absorbers, and other auxiliaries such as desiccants, flow agents and flow control agents, surfactants, or catalysts.
  • the plasticizer is preferably 1 to 5 parts, and the antioxidant is preferably 0.1 to 0.2 parts.
  • the plasticizer is one or more of epoxidized soybean oil, flaxseed oil, castor oil, and palm oil.
  • the antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(tridecyl)thiodipropionate, and pentaerythritol tetrakis ⁇ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ⁇ .
  • the pressure-sensitive adhesive product is an adhesive tape, adhesive stick, or film roll.
  • the pressure-sensitive adhesive product has an initial tack ball number of 5 or higher, and/or a 180° peel strength of 6 N/25 mm or higher, and/or a holding power of 84 h or higher, and/or a degradation rate of 87% or higher.
  • this application reacts the modified diol and amorphous carbon dioxide-based polyester diol with carboxyl-terminated polyester in a certain proportion to obtain a polyester-type resin.
  • This polyester-type resin contains carboxyl-terminated polyester segments, amorphous carbon dioxide-based polyester segments, and side chain segments.
  • the carboxyl-terminated polyester segments are hard segments that provide the cohesive strength required by the polyester-type resin, while the amorphous carbon dioxide-based polyester segments are soft segments that ensure the elasticity of the polyester-type resin.
  • the modified diol segments contain side chains that are incorporated into the polyester resin, thereby increasing the branching degree of the polyester resin, lowering the glass transition temperature, and enhancing the overall molecular chain mobility of the resin.
  • the ester bonds contained in the side chains can provide a large number of hydrogen bonds, making it easy to form hydrogen bond adhesion with the adhesive substrate, resulting in good initial tack.
  • the polyester resin is formulated into a polyester pressure-sensitive adhesive.
  • a tackifying resin may or may not be added. Even without the tackifying resin, the polyester pressure-sensitive adhesive exhibits strong cohesive properties and does not suffer from phase separation defects caused by poor compatibility between the tackifying resin and the matrix resin. Therefore, the peel strength and holding power of the pressure-sensitive adhesive can be improved.
  • the preferred polyester resin also possesses good biodegradability.
  • any lower limit can be combined with any upper limit to form an undefined range; and any lower limit can be combined with other lower limits to form an undefined range, just as any upper limit can be combined with any other upper limit to form an undefined range.
  • every point or individual value between the endpoints of a range is included within that range. Therefore, each point or individual value can serve as its own lower or upper limit and be combined with any other point or individual value, or with other lower or upper limits, to form an undefined range.
  • Diethanolamine was added to methanol, and isooctyl acrylate was added dropwise under inert gas N2 protection.
  • the reaction was carried out at 25 ⁇ 5°C for 24h, followed by at least three water washing and liquid-liquid extractions, and then methanol was removed by vacuum distillation to obtain modified diol 1; wherein the molar ratio of diethanolamine to isooctyl acrylate was 1.05:1.
  • Infrared spectroscopy was performed on modified diol 1 using a Nicolet iS50 Fourier transform infrared spectrometer (Thermo Fisher Scientific, USA), with a wavenumber range of 400-4000 cm ⁇ 1 and 32 scans. The sample was uniformly coated onto a dried KBr plate and analyzed using Fourier transform infrared spectroscopy.
  • the infrared spectrum is shown in Figure 1.
  • 3500 cm ⁇ 1 is the stretching vibration peak of -OH
  • 2956 cm ⁇ 1 and 2868 cm ⁇ 1 are the symmetric and asymmetric stretching vibration peaks of methylene
  • 1180 cm ⁇ 1 is the stretching vibration peak of -CN.
  • Diethanolamine and isooctyl acrylate underwent a Maillard addition reaction to obtain the target product.
  • Diethanolamine was added to methanol, and butyl acrylate was added dropwise under inert gas N2 protection.
  • the reaction was carried out at 25 ⁇ 5°C for 20h, followed by at least three water washing and liquid-liquid extractions, and then methanol was removed by vacuum distillation to obtain modified diol 2; wherein the molar ratio of diethanolamine to butyl acrylate was 1.2:1.
  • 2-Amino-1,3-propanediol was added to ethanol, and isooctyl acrylate was added dropwise under inert gas N2 protection.
  • the reaction was carried out at 25 ⁇ 5°C for 30 h, followed by at least three water washing and liquid-liquid extraction, and then ethanol was removed by vacuum distillation to obtain modified diol 3; wherein the molar ratio of 2-amino-1,3-propanediol to isooctyl acrylate was 1.1:1.
  • the method for determining the acid value is as follows: Dissolve an appropriate amount of sample thoroughly in 25 mL of chloroform solution, use phenolphthalein as an indicator, and titrate with 0.1 mol/L potassium hydroxide/ethanol standard solution until the solution turns red and remains so for 30 seconds.
  • the acid value X of the sample is calculated according to formula (1):
  • 56.1 is the molar mass of potassium hydroxide (g/mol);
  • X represents the acid value of the sample (mgKOH/g);
  • V1 is the volume (mL) of potassium hydroxide ethanol standard solution before titration;
  • V2 is the volume (mL) of potassium hydroxide ethanol standard solution after titration;
  • C is the concentration (mol/L) of potassium hydroxide ethanol standard solution; and
  • m is the weight (g) of the sample being titrated.
  • polypropylene carbonate diols described in the following examples were all purchased from Huizhou Daya Bay Dazhi Fine Chemical Co., Ltd. (Guangzhou Branch).
  • GPC test method The test was conducted using a Waters 1515 GPC instrument from the United States, with tetrahydrofuran (THF) as the mobile phase and a flow rate of 0.1 mL/min. Monodisperse polystyrene was used as the molecular weight correction standard.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 10:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 32,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 10:80:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 31,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 10:60:5. After heating to 130–150°C, a catalyst of 3 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, followed by cooling to room temperature to obtain a polyester resin with a molecular weight of approximately 28,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 15:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 33,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 20:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 35,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 10:90:10. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 33,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 10:90:20. After heating to 130–150°C, a catalyst of 8 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 3 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 30,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 2 were added to a reactor in a mass ratio of 10:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 2 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 32,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 3 were added to a reactor in a mass ratio of 10:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 3 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 32,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 2, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 10:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 2, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 29,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 3, polypropylene carbonate diol (molecular weight approximately 2,500), and the modified diol 1 were added to a reactor in a mass ratio of 10:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 3, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, followed by cooling to room temperature to obtain a polyester resin with a molecular weight of approximately 38,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 2,000), and the modified diol 1 were added to a reactor in a mass ratio of 10:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 30,000 as determined by GPC.
  • a polyester resin the preparation process of which is as follows:
  • Carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol (molecular weight approximately 4,000), and the modified diol 1 were added to a reactor in a mass ratio of 10:90:5. After heating to 130–150°C, a catalyst of 5 wt% of the total mass of the carboxyl-terminated polybutylene succinate 1, polypropylene carbonate diol, and the modified diol 1 was added. Polycondensation was carried out under a vacuum of 0.5 mmHg for 4 hours, and then cooled to room temperature to obtain a polyester resin with a molecular weight of approximately 35,000 as determined by GPC.
  • polyester-based pressure-sensitive adhesive The preparation process of polyester-based pressure-sensitive adhesive is as follows:
  • polyester resins described in Examples 1 to 13 were respectively formulated into polyester pressure-sensitive adhesives.
  • the specific formulations and preparation methods are as follows:
  • polyester resin 95 parts of polyester resin, 5 parts of epoxidized soybean oil and 0.15 parts of antioxidant tris(2,4-di-tert-butylphenyl) phosphite were stirred at 130°C for 3 hours. After cooling to room temperature, an appropriate amount of chloroform solution was added to obtain a pressure-sensitive adhesive solution with a solid content of 20 wt%.
  • the pressure-sensitive adhesive solution was coated onto a PET film using a coating machine. After being kept at 80°C for 10 minutes, the chloroform was evaporated, resulting in a pressure-sensitive adhesive layer with a thickness of approximately 15 ⁇ m.
  • Example 14 the polyester pressure-sensitive adhesive used is the polyester pressure-sensitive adhesive described in Example 1; in Example 15, the polyester pressure-sensitive adhesive used is the polyester pressure-sensitive adhesive described in Example 2; in Example 16, the polyester pressure-sensitive adhesive used is the polyester pressure-sensitive adhesive described in Example 3; ..., in Example 26, the polyester pressure-sensitive adhesive used is the polyester pressure-sensitive adhesive described in Example 13.
  • polyester-based pressure-sensitive adhesive The preparation process of polyester-based pressure-sensitive adhesive is as follows:
  • the pressure-sensitive adhesive solution was coated onto a PET film using a coating machine. After being kept at 80°C for 10 minutes, the chloroform was evaporated, resulting in a pressure-sensitive adhesive layer with a thickness of approximately 15 ⁇ m.
  • polyester-based pressure-sensitive adhesive The preparation process of polyester-based pressure-sensitive adhesive is as follows:
  • the pressure-sensitive adhesive solution was coated onto a PET film using a coating machine. After being kept at 80°C for 10 minutes, the chloroform was evaporated, resulting in a pressure-sensitive adhesive layer with a thickness of approximately 15 ⁇ m.
  • the test shall be conducted in accordance with Method A of GB/T 4851-2014.
  • the width of the biodegradable tape sample shall be 25 mm
  • the length of the bonding surface between the sample and the steel plate shall be (12 ⁇ 0.5 mm)
  • the mass of the weight shall be (1000 ⁇ 5 g).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Sont divulgués une résine de polyester, son procédé de préparation et un adhésif polyester sensible à la pression utilisant la résine de polyester. La résine de polyester comprend un copolymère d'un polyester à terminaison carboxyle, d'un polyester diol à base de dioxyde de carbone amorphe et d'un diol modifié, le rapport en poids dans des parties entre le polyester à terminaison carboxyle, le polyester diol à base de dioxyde de carbone amorphe et le diol modifié étant (10-30) : (50-99) : (2-30). Le procédé de préparation de la résine de polyester consiste : à placer des matières premières dans une cuve de réaction, à augmenter la température jusqu'à 100-180 °C, puis à ajouter un catalyseur en une quantité de 1 à 2 % de la masse totale des matières premières, et à réaliser une polycondensation et un refroidissement sous vide pour obtenir la résine de polyester.
PCT/CN2024/109570 2024-06-07 2024-08-02 Résine de polyester et procédé de préparation associé, adhésif polyester sensible à la pression et produit adhésif sensible à la pression Pending WO2025251404A1 (fr)

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