CN109504023A - A kind of thermoplastic elastomer (TPE) and preparation method thereof of adhesive glass - Google Patents
A kind of thermoplastic elastomer (TPE) and preparation method thereof of adhesive glass Download PDFInfo
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- CN109504023A CN109504023A CN201811472377.1A CN201811472377A CN109504023A CN 109504023 A CN109504023 A CN 109504023A CN 201811472377 A CN201811472377 A CN 201811472377A CN 109504023 A CN109504023 A CN 109504023A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of thermoplastic elastomer (TPE)s and preparation method thereof of adhesive glass, first, in accordance with the ratio of 3:1~1:3, SIS block copolymer and white oil are added in high-speed mixer, 5~10min of mixed at high speed, so that the abundant oil suction of SIS, then by 0~100 part of tackifier, 0~30 part of modifier, 0.5~3 part of scraping-resistant agent, 2-20 parts of antistatic agent, 0.1~2 part of antioxidant, 0~150 part of inorganic filler, 0~5 part of release agent sequentially adds in high-speed mixer, after 3~8min of mixed at high speed, it is transferred to double screw extruder, at 150~230 DEG C, pass through melt blending pelletizing, a kind of thermoplastic elastomer composite material of adhesive glass is made.Processing technology of the present invention is simple；The thermoplastic elastomer (TPE) of preparation, is easy to injection molding, can adhere at 170~230 DEG C to glass.
Description
Technical field
The present invention relates to a kind of preparation method of thermoplastic elastic material more particularly to a kind of thermoplastics of adhesive glass
Property method for producing elastomers, belongs to high molecular material blending and modifying field.
Background technique
Thermoplastic elastic material had both had the flexibility similar to conventional vulcanized rubbers, high resiliency, ageing-resistant, oil resistant
Property etc. every characteristic, while but also with the machinability of common plastics, referred to as third generation rubber.Its product category is abundant, contains
Multiple industrialization categories such as SBS, SIS, EVA, POE, TPU, TPAE, TPF are covered, due to its environmentally friendly, nontoxic, comfortable feel, processing
Simple process, it is recyclable the advantages that, as environmental-friendly novel high polymer material, be widely used in sole,
The multiple fields such as adhesive tape, cable, medical catheter and automobile interior decoration.Especially as soft rubber material, for PP, PC, POM,
The adherency of the rigid plastics such as PA is encapsulated, becomes increasingly prevalent in industry and civil field.And for unorganic glass or metal
It adheres to encapsulated, since its adhesion strength is very low, is unable to reach requirement, application does not almost relate to.Currently, exploitation can be with
Adherent glass, and the reachable or higher thermoplastic elastic material similar to adherency rigid plastics of adhesion strength, have it is theoretical and
Realistic meaning.
This technology invention uses SIS for basic material, is plasticizer by addition white oil, and addition Pioloform, polyvinyl acetal is to increase
Stick after being sufficiently mixed uniformly using high-speed mixer, is squeezed out simultaneously pelletizing through double screw extruder, a kind of adhesive glass is made
Thermoplastic elastic material, which has that soft, smooth, scratch resistance, antistatic, adherent glass be strong, easily injection molding adds
The features such as work, can be widely applied to the fields such as glass protection film.
Summary of the invention
A kind of thermoplastic elastomehc of adhesive glass is provided the invention aims to solve the problems, such as of the existing technology
Property body, improve elastomeric material adherent glass peel strength, to cope with market for glass protection soft elastomer material
Demand.
A kind of thermoplastic elastomer (TPE) and preparation method thereof of adhesive glass of the present invention, it is characterised in that preparation method is such as
Under, the amount of following substance is indicated with parts by weight:
First, in accordance with the ratio of 3:1~1:3, high-speed mixer, mixed at high speed 5 is added in SIS block copolymer and white oil
~10min, so that the abundant oil suction of SIS, then by 0~100 part of tackifier, 0~30 part of modifier, 0.5~3 part
Scraping-resistant agent, 2-20 parts of antistatic agent, 0.1~2 part of antioxidant, 0~150 part of inorganic filler, 0~5 part of release agent successively add
Enter in high-speed mixer, after 3~8min of mixed at high speed, be transferred to double screw extruder, at 150~230 DEG C, passes through melt blending
And pelletizing, a kind of thermoplastic elastomer composite material of adhesive glass is made.
SIS block copolymer of the present invention is the triblock copolymer of styrene-isoprene-phenylethene composition
Object, molecular structure are linear structure or star structure, and shore hardness is 20A~90A, the ratio of styrene/isoprene (S/I)
Example is 15/85~45/55, and molecular weight is 7~350,000,4111,4113,4114, the 4211 of main trade mark You Tai rubber company production
Etc. series.The preferred SIS trade mark is VECTOR 4111A, and appearance is in powdered, and S/I ratio is 18/82, and molecular structure is line
Property, shore hardness 39A, melt flow rate (MFR) is 12.0g/10min (190 DEG C/2.16kg), and tensile strength 30.5MPa breaks
Splitting elongation is 1300%.
White oil of the present invention is to add hydrogen paraffin oil, such as No. 10, No. 15, No. 26, No. 45, No. 50 white mineral oils,
(40 DEG C) of kinematic viscosity are 10~100cSt, and density is 0.75~0.90g/cm3, flash-point is 150~210 DEG C.Preferred white oil
For No. 26 paraffin oils of cosmetics-stage, (40 DEG C) of kinematic viscosity are 24.5~26.5cSt, density 0.85g/cm3, flash-point is
180 DEG C, appearance is colorless and odorless transparency liquid.
Tackifier of the present invention are that Polyvinyl acetal closes object, such as polyvinyl formal (PVF), polyethylene
Alcohol acetal (PVE), polyvinyl formal acetal (PVFE), polyvinyl butyral (PVB).Preferred tackifier are to glass
PVB with strong adhesive attraction, the trade mark mainly have Kuraray Corporation produce B20H, B30H, B30HH, B45H, B60H,
B60HH, B75H etc., white in appearance powder, density 1.07g/cm3, water absorption rate≤0.4%, ash content≤0.1%.
Modifier of the present invention is pure monomer Petropols, the pure monomer petroleum produced such as Yi Si Mann
The trades mark such as resin 3085,3100,3115,5140, A75, D125, viscosity average molecular weigh Mz >=1900, weight average molecular weight Mw >=
1100, softening point >=74 DEG C.Preferred pure monomer Petropols are highly viscous trade mark D125, and viscosity average molecular weigh Mz is
179000, weight average molecular weight Mw are 37400, and softening point is 126 DEG C.
Scraping-resistant agent of the present invention is boron nitride micro mist, silicon nitride powder, silicon carbide micro-powder, white fused alumina micro mist or poly-
Tetrafluoroethene micro mist.Preferred scraping-resistant agent is nanoscale silicon nitride powder, average grain diameter 20nm, purity >=99.9%,
White in appearance powder.
Antistatic agent of the present invention is powdered Polymer Antistatic Agent, such as the oxirane ring of ethylenediamine
Ethylene Oxide addition product, octyl styrene and styrene sulfonic acid copoly type polysoap, substance content >=99%.Preferably resist quiet
Electric agent is that the group of German Clariant Corporation production becomes compound based on ethylene oxide amine addition product, trade mark SAS93,
Type is nonionic surface active agent, and fusing point is 50 DEG C, and decomposition temperature >=300 DEG C, appearance is white powder, substance content
>=99%, amine value is 60~80mgKOH/ grams.
Antioxidant of the present invention is Hinered phenols antioxidant, such as antioxidant 1010,1076,1330,1135 or 245
Deng.Preferred Hinered phenols antioxidant is antioxidant 1010, and its chemical name is four [β-(3.5- di-t-butyl, 4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester, molecular weight 1177.6, fusing point is 110.0~125.0 DEG C, white in appearance crystalline powder.
Inorganic filler of the present invention be superfine titanium white, ultrafine mica powder, ultrafine kaolin, calcium carbonate superfine powder or
Superfine talcum powder, average grain diameter are micron order.Preferred inorganic filler is the superfine heavy calcium carbonate of food-grade.
Release agent of the present invention is stearic amide, and purity >=98%, appearance is white powder, and molecular weight is
283,96~102 DEG C of fusing point.
Double screw extruder of the present invention, draw ratio (L/D) >=48:1.Preferred above-mentioned twin-screw extrusion
Machine, L/D 56:1, cooling use sink tie rod mode.
A kind of process for preparation of thermoplastic elastomer of adhesive glass of the present invention, used formula for raw stock with plus
Work technique has a characteristic that
The present invention uses oil-filled SIS block copolymer for substrate, and the PVB by addition to glass with strong adhesive attraction is
A kind of thermoplastic elastomer (TPE) of adhesive glass is made through double screw extruder melting mixing in tackifier and other auxiliary agents.
The SIS and PVB compatibility that the elastic composite uses is good, high to the adhesion strength of glass, passes through the oil-filled ratio for adjusting SIS
Example, the hardness of adjustable composite material.It uses pure monomer Petropols for modifier, not only improves the molten of material
Melt mobility and injection molding processability, and plays certain auxiliary Efficient Adhesive Promotion.It is micro- by adding a certain amount of activated calcium carbonate
Powder is inorganic filler, not only reduces material cost, while improving the melt stability that material squeezes out processing.The elastomer material
Material uses double screw extruder, is made through one-step method melting mixing, processing technology is simple.
A kind of thermoplastic elastomer (TPE) of the adhesive glass prepared in the present invention, is easy to injection molding, can be 170~230
DEG C glass is adhered to.
Specific embodiment
The present invention is by the following specific embodiments described in more details technical solution of the present invention, but the present invention
It is not limited to specific embodiment proposed below.
Following embodiment and the comparative example raw materials trade mark, physical property are listed in table 1 in the present invention:
Table 1
A kind of thermoplastic elastic material of the adhesive glass obtained in the following examples and comparative examples, melt index
Using fusion index instrument, test condition is 190 DEG C, 2.16kg, tests five groups of samples altogether, and take its average value；The hardness of material,
It is tested using Shore durometer, reading when taking its 1 second；Its mechanical property is according to ASTM D638-89 standard 23 ± 2
It is tested at DEG C, tensile speed 500mm/min；The scratch resistance of material is tested, and is carried out according to DIN53516 standard；The stripping of material
GB2792 standard is used from intensity, the size (length/width/thickness) of adherent glass print is 150mm/25mm/2.0mm, the drawing of removing
Stretch speed selection 100mm/min；The antistatic property of material: surface resistivity and volume resistivity are according to GBT15662-1995
Standard carries out, test voltage 500V.
A kind of thermoplastic elastomer (TPE) of adhesive glass in embodiment described below and comparative example, using double screw extruder
Preparation, the draw ratio L/D of twin-screw are 56:1,180~210 DEG C of extrusion temperature；The elastomeric material adherent glass is in injection molding machine
Upper progress, 180~200 DEG C of injection temperature.
The embodiment of the present invention 1~4 and the formula composition of comparative example 5~9 are listed in Table 2 below:
Table 2
The embodiment of the present invention 1~4 and 5~9 test result of comparative example are listed in Table 3 with performance:
Table 3
Examples 1 to 4: using oil-filled SIS block copolymer for substrate, is tackifier by addition PVB, adds petroleum tree
Rouge is modifier, and addition nano-silicon nitride is scraping-resistant agent, and addition ethylene oxide amine additives are antistatic agent and other
Auxiliary agent, each component form be shown in Table 2 in detail.By table 3 it can be found that the test result of Examples 1 to 4 each group: its shore hardness≤
73A, tensile strength >=12.5MPa, peel strength >=9.5N/mm of adherent glass, surface resistivity≤9.0 × 1010Ω/sq,
Volume resistivity≤7.2 × 109Ω·cm.The thermoplastic elastic material of prepared adhesive glass, have material softness,
Feel is smooth, surface scratch resistance, it is antistatic it is good, adherent glass is strong, easy injection molding and the features such as easy mold release, can satisfy glass guarantor
The requirement of protective film material.
Comparative example 5~9: compared with embodiment 2 and embodiment 4, the composition and additive amount of substrate are remained unchanged, by dividing
It Tian Jia be not tackifier with EVA-250, EVA-40W, EAA-5986, EEA-2715AC, TPU-WHT1198 of PVB equivalent, and its
Its auxiliary agent can see Table 2 for details.The test result of comparative example 5~9 is can be found that by table 3: prepared elastomeric material, adherency
The peel strength of glass is all very low, respectively only 2.5N/mm, 2.8N/mm, 3.1N/mm, 1.9N/mm, 3.7N/mm, cannot be fine
The requirement for meeting glass protection membrane material.
Above embodiments show a kind of thermoplastic elastic material of adhesive glass prepared by the present invention, have fine
Comprehensive performance.
Disclosed above is only the several specific embodiments of the present invention, but the application is not limited to this, any in base of the present invention
On plinth, variation to the progress such as wherein formula composition, processing technology all should be in the application protection scope.
Claims (10)
1. a kind of thermoplastic elastomer (TPE) of adhesive glass, it is characterized in that: being prepared by following method:
On the basis of 100 parts of SIS, the amount of addition is indicated with parts by weight following substance:
First, in accordance with the ratio of 3:1~1:3, SIS block copolymer and white oil are added in high-speed mixer, mixed at high speed 5~
10min, so that the abundant oil suction of SIS, then by 0~100 part of tackifier, 0~30 part of modifier, 0.5~3 part resistance to
Scrape agent, 2-20 parts of antistatic agent, 0.1~2 part of antioxidant, 0~150 part of inorganic filler, 0~5 part of release agent sequentially add height
In fast mixing machine, after 3~8min of mixed at high speed, it is transferred to double screw extruder, at 150~230 DEG C, is cut by melt blending
Grain, is made a kind of thermoplastic elastomer composite material of adhesive glass.
2. a kind of process for preparation of thermoplastic elastomer of adhesive glass, it is characterized in that: following substance is using 100 parts of SIS as base
The amount of standard, addition is indicated with parts by weight:
First, in accordance with the ratio of 3:1~1:3, SIS block copolymer and white oil are added in high-speed mixer, mixed at high speed 5~
10min, so that the abundant oil suction of SIS, then by 0~100 part of tackifier, 0~30 part of modifier, 0.5~3 part resistance to
Scrape agent, 2-20 parts of antistatic agent, 0.1~2 part of antioxidant, 0~150 part of inorganic filler, 0~5 part of release agent sequentially add height
In fast mixing machine, after 3~8min of mixed at high speed, it is transferred to double screw extruder, at 150~230 DEG C, is cut by melt blending
Grain, is made a kind of thermoplastic elastomer composite material of adhesive glass.
3. the process for preparation of thermoplastic elastomer of a kind of adhesive glass according to claim 2, it is characterized in that: being adopted
SIS block copolymer is the triblock copolymer of styrene-isoprene-phenylethene composition, and molecular structure is line style
Structure or star structure, shore hardness are 20A~90A, and the ratio of styrene/isoprene is 15/85~45/55, molecular weight
It is 7~350,000.
4. the process for preparation of thermoplastic elastomer of a kind of adhesive glass according to claim 2, it is characterized in that: being adopted
White oil is plus hydrogen paraffin oil, kinematic viscosity at 40 DEG C are 10~100cSt, and density is 0.75~0.90g/cm3, is dodged
Point is 150~210 DEG C.
5. the process for preparation of thermoplastic elastomer of a kind of adhesive glass according to claim 2, it is characterized in that: being adopted
Tackifier are that Polyvinyl acetal closes object.
6. a kind of process for preparation of thermoplastic elastomer of adhesive glass according to claim 2, it is characterized in that: using
Modifier be pure monomer Petropols, viscosity average molecular weigh Mz >=1900, weight average molecular weight Mw >=1100, softening point >=
74℃。
7. the process for preparation of thermoplastic elastomer of a kind of adhesive glass according to claim 2, it is characterized in that: being adopted
Scraping-resistant agent is boron nitride micro mist, silicon nitride powder, silicon carbide micro-powder, white fused alumina micro mist or ptfe micropowder.
8. the process for preparation of thermoplastic elastomer of a kind of adhesive glass according to claim 2, it is characterized in that: being adopted
Antistatic agent is powdered Polymer Antistatic Agent, substance content >=99%.
9. the process for preparation of thermoplastic elastomer of a kind of adhesive glass according to claim 2, it is characterized in that being adopted
Antioxidant is Hinered phenols antioxidant；Used inorganic filler is superfine titanium white, ultrafine mica powder, ultra-fine kaolinite
Soil, calcium carbonate superfine powder or superfine talcum powder, average grain diameter are micron order.
10. the process for preparation of thermoplastic elastomer of a kind of adhesive glass according to claim 2, it is characterized in that: institute
The release agent used is stearic amide, purity >=98%, and appearance is white powder, molecular weight 283, fusing point 96~102
℃。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112538229A (en) * | 2020-12-22 | 2021-03-23 | 昆山六二丰塑胶电子有限公司 | High-strength wireless signal receiver injection molding material and formula |
| CN113248858A (en) * | 2021-04-26 | 2021-08-13 | 深圳市真味生物科技有限公司 | Disposable electronic cigarette holder kit and preparation method thereof |
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Application publication date: 20190322 |