CN112694857A - Modified polymerized terpene resin and preparation method thereof - Google Patents

Modified polymerized terpene resin and preparation method thereof Download PDF

Info

Publication number
CN112694857A
CN112694857A CN202011552913.6A CN202011552913A CN112694857A CN 112694857 A CN112694857 A CN 112694857A CN 202011552913 A CN202011552913 A CN 202011552913A CN 112694857 A CN112694857 A CN 112694857A
Authority
CN
China
Prior art keywords
modified
percent
polymerized
terpene resin
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
CN202011552913.6A
Other languages
Chinese (zh)
Inventor
崔程
王松
蔡钊亮
王琳
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.)
Songchuan Industrial Materials Wuxi Co ltd
Original Assignee
Songchuan Industrial Materials Wuxi 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 Songchuan Industrial Materials Wuxi Co ltd filed Critical Songchuan Industrial Materials Wuxi Co ltd
Priority to CN202011552913.6A priority Critical patent/CN112694857A/en
Publication of CN112694857A publication Critical patent/CN112694857A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • 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
    • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
    • 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
    • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09J157/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to an adhesive raw material and a preparation process thereof, in particular to a modified polymerized terpene resin and a preparation method thereof, which can increase the cohesion of a finished product, improve the initial strength and the retention of the adhesive, improve the process problems of brittleness, large dust and the like in the production process of polymerized terpene products, and comprise the following components in percentage by weight: 5 to 20 percent of styrene butadiene block copolymer A polymerized by a solvent method, 20 to 60 percent of beta-polymerized terpene resin B, 20 to 40 percent of aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin C, 10 to 20 percent of phenol modified terpene resin D, 0.1 to 1 percent of antioxidant E and 0.1 to 1 percent of antioxidant F; the adopted solvent method for polymerizing the styrene butadiene block copolymer A Sunpolymer S-0100 polymer provides excellent initial viscosity, holding power and toughness, so that the problem of overlarge dust during granulation of most resins is solved; the beta-polymerized terpene resin provides excellent adhesion and holding power and has excellent heat resistance.

Description

Modified polymerized terpene resin and preparation method thereof
Technical Field
The invention relates to an adhesive raw material and a preparation process thereof, in particular to a modified polymerized terpene resin and a preparation method thereof.
Background
Polymerized terpene resins have good tack, compatibility, thermal stability and light stability, and can improve the adhesive properties and holding power of adhesives, and are essential tackifying components for many adhesives. The terpene resin is modified to obtain the terpene resin with better performance, and has stronger viscosity, higher retentivity and initial viscosity and better toughness than the common terpene resin.
At present, a rotary belt type condensation granulator used for common petroleum resin is selected for granulation of the product, and due to the fact that the viscosity is high, the hydrogenated petroleum resin is firmly adhered to a stainless steel belt by cooling a granulation tail end of a conventional rotary belt granulator in a 200 ℃ molten state, a scraper is adopted to scrape off the resin attached to the steel belt, most of the resin formed by granulation is broken, and the quality of the product is greatly reduced.
Disclosure of Invention
In view of the problems mentioned in the background art, the present invention aims to provide a modified polymerized terpene resin and a preparation method thereof, which can increase the cohesion of the finished product and improve the initial strength and the retention of the adhesive, and improve the process problems of brittleness, large dust, etc. in the production process of the polymerized terpene product.
The technical purpose of the invention is realized by the following technical scheme: a modified polymerized terpene resin comprises the following components in parts by weight: 5 to 20 percent of styrene butadiene block copolymer A polymerized by a solvent method, 20 to 60 percent of beta-polymerized terpene resin B, 20 to 40 percent of aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin C, 10 to 20 percent of phenol modified terpene resin D, 0.1 to 1 percent of antioxidant E and 0.1 to 1 percent of antioxidant F.
Preferably, the solvent-process polymerized styrene butadiene block copolymer A is Sunpolymer S-0100.
Preferably, the β -polymerized terpene resin B is one of SuntackSR105 and SuntackSR 120.
Preferably, the aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin C is SuntackHW-100P.
Preferably, the phenol-modified terpene resin D is one of SYLVARESTP2040HM and SYLVARESTP 96.
Preferably, the antioxidant E is 1010.
Preferably, the antioxidant F is 168.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of modified polymerized terpene comprises the following reaction steps:
step one, pretreating and processing a solvent-method polymerized styrene-butadiene block copolymer A Sunpolymer S-0100 by using a kneader, and melting the solvent-method polymerized styrene-butadiene block copolymer A Sunpolymer S-0100;
step two, firstly adding aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin C SuntackHW-100P, an antioxidant E1010 and an antioxidant F168 into a reaction kettle for pre-melting, after the resin is completely melted, adding a solvent method polymerized styrene butadiene block copolymer A Sunpolymer S-0100 in batches in equal parts and three times, after the copolymer is completely melted, adding beta-polymerized terpene resin B, and after the copolymer is completely melted, adding phenol modified terpene resin D;
and step three, vacuumizing the reactor after the materials are completely put into the reactor, wherein the vacuum coefficient is less than-0.08, and discharging the materials after the materials are continuously stirred for 30min at the material temperature of 140 ℃.
In summary, the invention mainly has the following beneficial effects: the modified polymerized terpene resin and the preparation method thereof adopt a solvent method to polymerize the styrene butadiene block copolymer A Sunpolymer S-0100 polymer, provide excellent initial viscosity and retention and toughness, and solve the problem of overlarge dust during the granulation of most resins; the beta-polymerized terpene resin provides excellent adhesion and retention and has excellent heat resistance; the phenol modified terpene resin increases the initial viscosity of the polymerized terpene resin to polar base materials, and improves the softening point; the aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin improves the heat resistance and aging resistance of the polymerized terpene resin.
The modified polymerized terpene resin and the preparation method thereof can effectively solve the problems that the common polymerized terpene resin has overlarge dust, larger resin brittleness and serious appearance breakage during production, and the production and use of customers are influenced, and the common polymerized terpene resin can not increase the cohesion of finished products of the customers and improve the initial strength of the adhesive.
The SuntackSR110P production process is simple and effective, can save a large amount of energy consumption, does not generate hazardous waste, and has good environmental protection, economic benefit and industrial production prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: heating a reaction kettle to 165 ℃, adding naphthenic oil KN-4010130 g, an antioxidant 1010 and 168, each 0.5g of a stirring paddle, rotating at the speed of 100r/min, preheating and stirring for 10min, adding SIS rubber D1111100 g, preheating and stirring for 10min, adding the petroleum resin SU-100150 g after the SIS rubber D1111 is fully pre-melted, continuously preheating and stirring for 20min, adding the SIS rubber D1111100 g after the petroleum resin is fully melted into a liquid state, continuously stirring for about 10min, adding the modified polymerized terpene resin SUNTACKSR110P170g, melting, adding the SIS rubber D1111150 g, vacuumizing until the vacuum coefficient is less than or equal to-0.08, continuously observing the rubber dissolution state for 1h, adding the petroleum resin SU-100200 g, and discharging after the petroleum resin SU-100200 g is fully melted. The whole formulation trial time is controlled within 2.5 h.
The experimental data are as follows in table 1:
Figure BDA0002857705980000051
remarking: TC-A is a polymeric terpene resin formulation modified with SUNTACKSR 110P.
TC-B is a formula of modified polymerized terpene resin using a certain conventional equivalent SP.
Example 2: heating a reaction kettle to 165 ℃, adding naphthenic oil KN-4010130 g, an antioxidant 1010 and 168, each 0.5g of a stirring paddle, rotating at the speed of 100r/min, preheating and stirring for 10min, adding SIS rubber D1111100 g, preheating and stirring for 10min, adding the petroleum resin SU-100150 g after the SIS rubber D1111 is fully pre-melted, continuously preheating and stirring for 20min, adding the SIS rubber D1111100 g after the petroleum resin is fully melted into a liquid state, continuously stirring for about 10min, adding the modified polymerized terpene resin SUNTACKSR110P200g, melting, adding the SIS rubber D1111150 g, vacuumizing until the vacuum coefficient is less than or equal to-0.08, continuously observing the rubber dissolution state for 1h, adding the petroleum resin SU-100170 g, and discharging after the petroleum resin SU-100170 g is fully melted. The whole formulation trial time is controlled within 2.5 h.
The experimental data are as follows in table 2:
Figure BDA0002857705980000061
remarking: TC-C uses 3% more SUNTACKSR110P modified polymerized terpene resin than TC-A and 3% less petroleum resin SU-100 formulation (other ingredients unchanged).
The performance of the SUNTACKSR110P modified polymerization terpene resin in the aspects of heat resistance, retention, initial adhesion and the like is completely superior to that of a certain conventional terpene resin, the cost is controllable, a large amount of energy consumption can be saved in the aspect of process, no hazardous waste is generated, and the modified polymerization terpene resin has good environmental protection, economic benefit and industrial production prospect.
The performance of initial adhesion, holding power, stripping force and the like can also be improved by adding SUNTACKSR110P modified polymerized terpene resin in the same proportion.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. A modified polymeric terpene resin characterized by: comprises the following components in parts by weight: 5 to 20 percent of styrene butadiene block copolymer A polymerized by a solvent method, 20 to 60 percent of beta-polymerized terpene resin B, 20 to 40 percent of aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin C, 10 to 20 percent of phenol modified terpene resin D, 0.1 to 1 percent of antioxidant E and 0.1 to 1 percent of antioxidant F.
2. The modified polymeric terpene resin of claim 1 wherein: the solvent method polymerized styrene butadiene block copolymer A is Sunpolymer S-0100.
3. The modified polymeric terpene of claim 1, wherein: the beta-polymerized terpene resin B is one of SuntackSR105 and SuntackSR 120.
4. The modified polymeric terpene of claim 1, wherein: the aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin C is SuntackHW-100P.
5. The modified polymeric terpene of claim 1, wherein: the phenol modified terpene resin D is SYLVARESTP2040HM, SYLVARESTP 96.
6. The modified polymeric terpene of claim 1, wherein: the antioxidant E is 1010.
7. The modified polymeric terpene of claim 1, wherein: the antioxidant F is 168.
8. A process for the preparation of a modified polymeric terpene as claimed in any one of claims 1 to 7, characterized in that: the method comprises the following reaction steps:
step one, pretreating and processing a solvent-method polymerized styrene-butadiene block copolymer A Sunpolymer S-0100 by using a kneader, and melting the solvent-method polymerized styrene-butadiene block copolymer A Sunpolymer S-0100;
heating a reaction kettle to 165 ℃, adding naphthenic oil KN-4010, adding aromatic hydrocarbon modified dicyclopentadiene hydrogenated petroleum resin C SuntockHW-100P, antioxidant E1010 and antioxidant F168 into the reaction kettle for pre-melting, adding the styrene butadiene block copolymer A Sunpolymer S-0100 in three batches in equal batches after the resin is completely melted, adding beta-polymerized terpene resin B after the copolymer is completely melted, and adding phenol modified terpene resin D after the copolymer is completely melted;
and step three, vacuumizing the reactor after the materials are completely put into the reactor, wherein the vacuum coefficient is less than-0.08, and discharging the materials after the materials are continuously stirred for 30min at the material temperature of 140 ℃.
CN202011552913.6A 2020-12-24 2020-12-24 Modified polymerized terpene resin and preparation method thereof Pending CN112694857A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011552913.6A CN112694857A (en) 2020-12-24 2020-12-24 Modified polymerized terpene resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011552913.6A CN112694857A (en) 2020-12-24 2020-12-24 Modified polymerized terpene resin and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112694857A true CN112694857A (en) 2021-04-23

Family

ID=75510083

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011552913.6A Pending CN112694857A (en) 2020-12-24 2020-12-24 Modified polymerized terpene resin and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112694857A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000119636A (en) * 1998-10-19 2000-04-25 Yokohama Rubber Co Ltd:The Adhesive sealing material composition and sealing method using the same
CN105969272A (en) * 2016-07-29 2016-09-28 无锡市万力粘合材料股份有限公司 Hot melt adhesive composition for cold storage label and preparation method thereof
CN106085309A (en) * 2016-07-29 2016-11-09 无锡市万力粘合材料股份有限公司 Automobile floor leather melt pressure sensitive glue composition and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000119636A (en) * 1998-10-19 2000-04-25 Yokohama Rubber Co Ltd:The Adhesive sealing material composition and sealing method using the same
CN105969272A (en) * 2016-07-29 2016-09-28 无锡市万力粘合材料股份有限公司 Hot melt adhesive composition for cold storage label and preparation method thereof
CN106085309A (en) * 2016-07-29 2016-11-09 无锡市万力粘合材料股份有限公司 Automobile floor leather melt pressure sensitive glue composition and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李广宇等: "《胶黏剂原材料手册》", 31 August 2004, 国防工业出版社 *

Similar Documents

Publication Publication Date Title
CN111019575B (en) High-temperature-resistant high-peeling-resistance hot-melt pressure-sensitive adhesive and preparation method thereof
US4514554A (en) Petroleum resin and pressure sensitive adhesive formulations utilizing same as tackifier
CA2176592C (en) Radial styrene-isoprene-butadiene multi-armed block copolymers and compositions and articles containing block copolymers
US4288567A (en) Adhesive composition and method of preparation
CN109054688B (en) Heat aging non-sticking hot melt pressure-sensitive adhesive and preparation method thereof
CN103694934B (en) A kind of hot-fusible pressure-sensitive adhesive and preparation method thereof
CN110734719A (en) Modified hot-melt pressure-sensitive adhesive and preparation method thereof
CN110003828A (en) Hot-fusible pressure-sensitive adhesive and preparation method thereof
CN111607344A (en) Oil-seepage-resistant low-temperature-resistant high-peeling-force hot-melt pressure-sensitive adhesive and preparation method thereof
CN114163975B (en) Hot-melt pressure-sensitive adhesive and preparation method and application method thereof
CN114163954A (en) Hot-melt pressure-sensitive adhesive for RFID (radio frequency identification) electronic tag and preparation method thereof
EP0149909A2 (en) Novel hydrocarbon resins and their use in adhesives
US20060223948A1 (en) Process for the production of hydrogenated petroleum resin
CN114525094A (en) Hot melt adhesive for bonding high-temperature-resistant food bags and preparation method thereof
CN112694857A (en) Modified polymerized terpene resin and preparation method thereof
EP2336242B1 (en) Mixture of conjugated diene - vinyl aromatic hydrocarbon copolymers and adhesive composition having the same
CN110746907B (en) Hot-melt pressure-sensitive adhesive suitable for bonding polyolefin woven cloth and metal plate and preparation method thereof
CN115851189A (en) Hot-melt pressure-sensitive adhesive for heat-resistant high-viscosity woven fabric adhesive tape and preparation method thereof
CN115537136B (en) Recoverable granulating composite protective film and recovery method
CN111944453B (en) Process method for preparing hot melt adhesive
CN114262602A (en) Hot melt adhesive for high-temperature protective clothing and preparation method thereof
CN102234362A (en) Styrene-isoprene hyperbranched copolymer and preparation method and application thereof
KR101706869B1 (en) Coupling agent of hemiacetal ester group, styrene-butadiene block copolymer using the same, and hot-melt adhesive composition comprising the same
CN115449341A (en) Plasticizer-free hot-melt pressure-sensitive adhesive capable of being coated at low temperature and preparation method thereof
CN117801689A (en) Hot-melt pressure-sensitive adhesive with good bonding effect and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210423

RJ01 Rejection of invention patent application after publication