CN105778836A - Amorphous block copolymer-modified polyvinyl adhesive - Google Patents

Amorphous block copolymer-modified polyvinyl adhesive Download PDF

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Publication number
CN105778836A
CN105778836A CN201610228889.8A CN201610228889A CN105778836A CN 105778836 A CN105778836 A CN 105778836A CN 201610228889 A CN201610228889 A CN 201610228889A CN 105778836 A CN105778836 A CN 105778836A
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China
Prior art keywords
block copolymer
armorphous
polyethylene
extruder
glue
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CN201610228889.8A
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Chinese (zh)
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CN105778836B (en
Inventor
夏浙安
李欣欣
李旭华
唐宇航
习志亮
俞冰
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Long Zhi Yao Zhejiang New Mstar Technology Ltd
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Suzhou Longzhi Yaoxin Materials Co Ltd
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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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • 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

Abstract

The invention discloses an amorphous block copolymer-modified polyvinyl adhesive.A reactive blending process is implemented through twin-screw extrusion for extrusion granulating preparation.The amorphous block copolymer-modified polyvinyl adhesive is prepared from, by weight, 70-95% of polyethylene graft bonding resin, 4-25% of an amorphous block copolymer and 0.5-5% of a compatibilizer.The amorphous block copolymer-modified polyvinyl adhesive has a high vicat softening point temperature and can be applied to various fields such as pipeline corrosion prevention, oil and gas delivery and municipal drainage.

Description

A kind of armorphous block copolymer-modified polyethylene glue
Technical field
The present invention relates to a kind of armorphous block copolymer-modified polyethylene glue, specifically, be a kind of preparation method being implemented polycthylene grafted thing adhering resin and armorphous block copolymer resin reactive blending by double screw extruder.
Background technology
Polyethylene glue has a wide range of applications in fields such as pipeline corrosion protection, oil-gas transportation, municipal drainages at present.China Patent No. CN102533162A describes the preparation method of a kind of 3PE anti-corrosion pipeline PE PUR powder.Polycthylene grafted thing adhering resin, polyolefin base resin, elastomer tackifier resins, levelling agent by twin-screw extrusion, are implemented composite technique extruding pelletization, and obtained PE PUR powder by milling equipment.China Patent No. CN102399519A describes a kind of composite metal plastic pipe PUR and production method.Being prepared for one with high density polyethylene (HDPE), maleic anhydride, peroxide, antioxidant etc. and meet rower CJ/T225-2006, peel strength is up to standard, and ring flexibility is qualified, the polyethylene hot-melt adhesive that solar exposure is qualified.Above traditional special polyethylene glue is based on high density polyethylene (HDPE) (HDPE), Low Density Polyethylene (LDPE).In order to promote the vicat temperature of polyethylene glue, often high density polyethylene (HDPE) usage ratio is relatively big, and owing to high density polyethylene (HDPE) degree of crystallinity is high, fusing point is high, and environmental stress crack resistance is poor.Too much high density polyethylene (HDPE) can cause PUR the most crisp, affects peel strength.
Summary of the invention
For solving the problem of above-mentioned existence, it is an object of the invention to provide a kind of armorphous block copolymer-modified polyethylene glue, the problem solving polycthylene grafted thing adhering resin and the poor compatibility of styrene maleic anhydride copolymer.The polyethylene glue vicat temperature prepared by reactive blending of the present invention is up to more than 110 DEG C.The polyethylene glue that the present invention obtains may be used for the numerous areas such as pipeline corrosion protection, oil-gas transportation, municipal drainage.
For reaching above-mentioned purpose, the present invention includes following technical scheme:
A kind of armorphous block copolymer-modified polyethylene glue, using twin-screw extrusion to implement reactive blending technique extruding pelletization to prepare, described a kind of armorphous block copolymer-modified polyethylene glue comprises each raw material components of following weight percentage: polycthylene grafted thing adhering resin: 70-95wt%；Armorphous block copolymer: 4-25wt%；Bulking agent: 0.5-5wt%.
Further, the preparation technology of described polycthylene grafted thing adhering resin is: with polyethylene mixture as matrix resin；The double screw extruder using nine sections of cartridge heaters makees flow reactor；Extruder heating barrel temperatures is set, is respectively along extrusion direction, 70 ~ 80 DEG C, 150 ~ 170 DEG C, 170 ~ 190 DEG C, 170 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 195 DEG C；Screw speed 90 ~ 110r/min；Cartridge heater reaches predetermined temperature, and from being positioned at the main charge door of extruder first paragraph, 3 ~ 6kg polyethylene compound is added extruder, and rate of feeding is 0.1 ~ 0.2kg/min；Maleic anhydride and peroxide initiator are dissolved in acetone, are injected with 0.001 ~ 0.008kg/min from the 3rd section of liquid addition port of extruder by pipeline and dosing pump；The lower melting graft reaction extrusion of heating obtains polycthylene grafted adhesive resin.
Separately, described polyethylene mixture one or more mixture in high density polyethylene (HDPE), Low Density Polyethylene, linear low density polyethylene, ethylene-octene copolymer.
Separately have, described peroxide initiator selected from benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide compound, 2,5-dimethyl-2, the mixture of one or more in 5-di-t-butyl hexane peroxide, peroxidized t-butyl perbenzoate.
Again, described each raw material proportioning in terms of weight fraction is: polyethylene mixture 100 parts, maleic anhydride 0.2-3 part, peroxide initiator 0.02-0.25 part, acetone 1-6 part.
Further, described armorphous block copolymer is styrene maleic anhydride copolymer.
And, described bulking agent is multi-epoxy chain extender.
The present invention has the beneficial effects that:
The features such as armorphous block copolymer-modified polyethylene glue prepared by the present invention can be used for the fields such as pipeline corrosion protection, has processing technique simple, good product performance.
The invention provides a kind of armorphous block copolymer-modified polyethylene glue, use twin-screw extrusion to implement reactive blending technique extruding pelletization and prepare.Described a kind of armorphous block copolymer-modified polyethylene glue comprises each raw material components of following weight percentage: polycthylene grafted thing adhering resin: 70%-95%；Armorphous block copolymer: 5%-25%；Bulking agent: 0.1%-5%.By polycthylene grafted thing adhering resin and the armorphous block copolymer of one (styrene maleic anhydride copolymer) are blended the vicat temperature that on the premise of ensureing its adhesive property, can improve polyethylene glue, effect is suitable with crystal type high density polyethylene (HDPE).The polyethylene glue vicat temperature prepared by reactive blending of the present invention is up to more than 110 DEG C.The features such as the polyethylene glue that the present invention obtains may be used for the numerous areas such as pipeline corrosion protection, oil-gas transportation, municipal drainage, has processing technique simple, good product performance.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be carried out clear, complete description below, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained on the premise of not making creative work, broadly fall into the scope of protection of the invention.
Embodiment one
Under room temperature, by 100g maleic anhydride and 4g 2,5-dimethyl-2,5-di-t-butyl hexane peroxide is dissolved in 100g acetone.3kg high density polyethylene (HDPE) and 2kg linear low density polyethylene mix homogeneously are added feeding bucket.Extruder heating barrel temperatures is set, is respectively along extrusion direction, 75 DEG C, 160 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 85 DEG C, 185 DEG C, 185 DEG C, 190 DEG C；Screw speed 100 r/min.Cartridge heater reaches predetermined temperature, and from being positioned at extruder first paragraph main charge door, 5kg polyethylene compound is added extruder, and rate of feeding is 0.15kg/min；Being injected with the speed of 0.002kg/min from the 3rd section of liquid addition port of extruder by dosing pump by acetone soln containing maleic anhydride and initiator, extrusion obtains polycthylene grafted thing adhering resin simultaneously.After polycthylene grafted for 4kg thing adhering resin, 0.4kg styrene maleic anhydride copolymer (SMA), 0.025 kg epoxy chain extenders (ADR) mix homogeneously, obtaining polyethylene glue granule by extruder extrusion, its vicat temperature is 110 DEG C.
Embodiment two
Under room temperature, by 100g maleic anhydride and 8g 2,5-dimethyl-2,5-di-t-butyl hexane peroxide is dissolved in 100g acetone.3kg high density polyethylene (HDPE) and 2 kg ethylene-octene copolymer mix homogeneously are added feeding bucket.Extruder heating barrel temperatures is set, is respectively along extrusion direction, 75 DEG C, 160 DEG C, 180 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 190 DEG C；Screw speed 100 r/min.Cartridge heater reaches predetermined temperature, and from being positioned at extruder first paragraph main charge door, 5kg polyethylene compound is added extruder, and rate of feeding is 0.15kg/min；Being injected with the speed of 0.006kg/min from the 3rd section of liquid addition port of extruder by dosing pump by acetone soln containing maleic anhydride and initiator, extrusion obtains polycthylene grafted thing adhering resin simultaneously.After polycthylene grafted for 4kg thing adhering resin, 1kg styrene maleic anhydride copolymer (SMA), 0.05kg epoxy chain extenders (ADR) mix homogeneously, obtaining polyethylene glue granule by extruder extrusion, vicat temperature is 112 DEG C.
The above is the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, without departing from the scope of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (7)

1. an armorphous block copolymer-modified polyethylene glue, use twin-screw extrusion to implement reactive blending technique extruding pelletization to prepare, it is characterised in that: described a kind of armorphous block copolymer-modified polyethylene glue comprises each raw material components of following weight percentage: polycthylene grafted thing adhering resin: 70-95wt%；Armorphous block copolymer: 4-25wt%；Bulking agent: 0.5-5wt%.
Armorphous block copolymer-modified polyethylene glue the most according to claim 1, it is characterised in that: the preparation technology of described polycthylene grafted thing adhering resin is: with polyethylene mixture as matrix resin；The double screw extruder using nine sections of cartridge heaters makees flow reactor；Extruder heating barrel temperatures is set, is respectively along extrusion direction, 70 ~ 80 DEG C, 150 ~ 170 DEG C, 170 ~ 190 DEG C, 170 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 190 DEG C, 180 ~ 195 DEG C；Screw speed 90 ~ 110r/min；Cartridge heater reaches predetermined temperature, and from being positioned at the main charge door of extruder first paragraph, 3 ~ 6kg polyethylene compound is added extruder, and rate of feeding is 0.1 ~ 0.2kg/min；Maleic anhydride and peroxide initiator are dissolved in acetone, are injected with 0.001 ~ 0.008kg/min from the 3rd section of liquid addition port of extruder by pipeline and dosing pump；The lower melting graft reaction extrusion of heating obtains polycthylene grafted adhesive resin.
Armorphous block copolymer-modified polyethylene glue the most according to claim 2, it is characterised in that: described polyethylene mixture one or more mixture in high density polyethylene (HDPE), Low Density Polyethylene, linear low density polyethylene, ethylene-octene copolymer.
Armorphous block copolymer-modified polyethylene glue the most according to claim 2, it is characterized in that: described peroxide initiator selected from benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide compound, 2,5-dimethyl-2, the mixture of one or more in 5-di-t-butyl hexane peroxide, peroxidized t-butyl perbenzoate.
Armorphous block copolymer-modified polyethylene glue the most according to claim 2, it is characterized in that: described each raw material proportioning in terms of weight fraction is: polyethylene mixture 100 parts, maleic anhydride 0.2-3 part, peroxide initiator 0.02-0.25 part, acetone 1-6 part.
Armorphous block copolymer-modified polyethylene glue the most according to claim 1, it is characterised in that: described armorphous block copolymer is styrene maleic anhydride copolymer.
Armorphous block copolymer-modified polyethylene glue the most according to claim 1, it is characterised in that: described bulking agent is multi-epoxy chain extender.
CN201610228889.8A 2016-04-14 2016-04-14 A kind of armorphous block copolymer-modified polyethylene glue Active CN105778836B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020156993A1 (en) * 2019-01-28 2020-08-06 Borealis Ag Process for producing a polymer composition
KR20210120028A (en) * 2019-01-28 2021-10-06 보레알리스 아게 polymer composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161730A (en) * 2010-12-30 2011-08-24 曲阜市东宏实业有限公司 Special adhesive resin for wire-frame-reinforced polyethylene tube and production method thereof
CN102190984A (en) * 2011-04-08 2011-09-21 河北金天塑胶新材料有限公司 Hot-melt adhesive for steel-plastic composite pipe
CN102533162A (en) * 2011-12-28 2012-07-04 广州鹿山新材料股份有限公司 Preparation method of poly ethylene (PE) hot melt glue powder for 3PE anti-corrosion pipelines
CN103232825A (en) * 2013-04-09 2013-08-07 顺德职业技术学院 Elastomer-based hot-melt adhesive and preparation method thereof
CN103361008A (en) * 2012-04-02 2013-10-23 上海通悦包装材料有限公司 Preparation method of hot melt adhesive composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161730A (en) * 2010-12-30 2011-08-24 曲阜市东宏实业有限公司 Special adhesive resin for wire-frame-reinforced polyethylene tube and production method thereof
CN102190984A (en) * 2011-04-08 2011-09-21 河北金天塑胶新材料有限公司 Hot-melt adhesive for steel-plastic composite pipe
CN102533162A (en) * 2011-12-28 2012-07-04 广州鹿山新材料股份有限公司 Preparation method of poly ethylene (PE) hot melt glue powder for 3PE anti-corrosion pipelines
CN103361008A (en) * 2012-04-02 2013-10-23 上海通悦包装材料有限公司 Preparation method of hot melt adhesive composition
CN103232825A (en) * 2013-04-09 2013-08-07 顺德职业技术学院 Elastomer-based hot-melt adhesive and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020156993A1 (en) * 2019-01-28 2020-08-06 Borealis Ag Process for producing a polymer composition
CN113329858A (en) * 2019-01-28 2021-08-31 博里利斯股份公司 Process for producing polymer composition
KR20210120028A (en) * 2019-01-28 2021-10-06 보레알리스 아게 polymer composition
CN113329858B (en) * 2019-01-28 2024-01-12 博里利斯股份公司 Method for producing a polymer composition
KR102633308B1 (en) * 2019-01-28 2024-02-06 보레알리스 아게 polymer composition

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