CN102241865B - Blend-type interpenetrating network thermoplastic elastomer TIEN (thermoplastic interpenetrating elastomer network) - Google Patents
Blend-type interpenetrating network thermoplastic elastomer TIEN (thermoplastic interpenetrating elastomer network) Download PDFInfo
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Abstract
The invention relates to a blend-type interpenetrating network thermoplastic elastomer. During the development history of TPE (thermoplastic elastomer), the TPE in an interpenetrating network structure is prepared from SEBS (styrene-ethylene/butylene-styrene block copolymer; P1), EPDM (ethylene propylene diene monomer; P2) and PP (polypropylene; P3) which are used as three blending components for the first time; an interpenetrating polymer network (IPN) technique and an interpenetrating elastomer network (IEN) technique are combined to be applied in the TIEN for the first time; in the TIEN, the initial network P1 and P2 chemical cross-linking network generated during dynamic vulcanization interpenetrate eachother in an interfacial layer to form the IEN, and P3 crystallizes and nearly fills the entire system to form a P1/P2 shared network; and the multi-phase system formed by the P1/P2/P3 interpenetrating network is stable and firm, has a cellular structure of the majority of IPN materials and the cellular structure is different from the block structure or 'sea-island' structure of the traditional TPE, and has better mechanical properties and processing moldability than any component and the TPE with SEBS or EPDM used as a base material.
Description
Technical field
The present invention relates to a kind of blending thermoplastic elastomer (international general designation TPE; Hereinafter to be referred as TPE); Especially the thermoplastic elastomer that a kind of elastomerics (rubber) network runs through each other; Be referred to as the commixed type interpenetrating network thermoplastic elastomer, be called for short TIEN (Therom Interpeneraeing Elastome Netuork).
Background technology
On world TPE development history, it is blend three components and the thermoplastic elastomer that runs through network each other by SEBS (styrene-ethylene/butylene-styrene block copolymer), EPDM (terpolymer EP rubber), PP (isotatic polypropylene) that the present invention makes a kind of first; First interpenetrating polymer networks (IPN) and elasticity interpenetrating(polymer)networks new technologies such as (IEN) are combined to be applied to blending thermoplastic elastomer.
In TIEN; The chemically crosslinked network that the cross-linked network of elastomerics SEBS (hereinafter to be referred as P1) and EPDM (hereinafter to be referred as P2) generate in blending reaction runs through, forms the IPN (Intepeneraeing Elasteme Netuork. is hereinafter to be referred as IEN) of elastomerics (rubber) network each other; And the crystallization of another component PP (hereinafter to be referred as P3) promptly almost is full of whole system; Become the shared network (claiming public network again) of P1/P2; This multiphase system that is formed by the P1/P2/P3 interpenetrating(polymer)networks is stable and firmly; Have remarkable thermoplasticity processing characteristics, mechanical property is superior to the arbitrary component in the blend components, and also being superior to all is the TPE or the mixture of base material with SEBS (claiming TPR again) or EPDM.
Interpenetrating polymer networks (Intepeneraeing Polymer Netnork is hereinafter to be referred as IPN) is the frontier of present high molecular polymer modification, and many different preparation and kind are arranged, and IEN is one of them branch.
At present; The thermoplastic elastomer of known all trades mark in the world (TPE) is mainly block structure or " sea-island " structure; As polyolefins thermoplastic elastomer (TPE-O), styrene analog thermoplastic elastomer (TPE-S), polyurethanes thermoplastic elastomer (TPE-U), polyester thermoplastic elastomer (TPE-E), polyamide-based thermoplastic elastomer (TPE-A), commixed type SE analog thermoplastic elastomer (TPVC) and various TPV (TPV) as: dynamic vulcanization type thermoplasticity paracril (TPNBR), dynamic vulcanization type thermoplasticity ethylene-propylene diene copolymer (EPDM/PP TPV), dynamic vulcanization type thermoplastic natural rubber (TPNR) and thermoplastic silicone, organic fluorine class elastomerics etc. do not have blend components and run through network, the particularly structure of elastomerics interpenetrating(polymer)networks each other.
In addition; Known all IPN materials in the world; Particularly with the relevant IPN of elastomerics (rubber); Like IPN NR/PS (natural gum/PS), IPN NR/PMMA (natural gum/polymethylmethacrylate), IPN CR/PS (neoprene latex/PS), IPN SBR/PS (butadiene-styrene rubber/PS), IPN NBR/PVA (butadiene-acrylonitrile rubber/polyvinylacetate), IPN PU/PS (urethane/PS), IPN PU/PMMA (urethane/polymethylmethacrylate), IPN PU/EP (polyurethane/epoxy resin), U.S.'s shell (Shell) company trade mark is that styrenic interpenetrating network thermoplastic elastomer, the U.S. PetrarchSystems company trade mark of KratonGX-7500 system is that semi-intercrossing network (Semi-IPN) polyurethane termoplastic elastomer, the trade mark of Rimplast PTUE series is that thermoplastic polyamide elastomer, company of Du Pont (DuPont) trade mark of PTA series is that IPN and the interpenetrating network thermoplastic polyester elastomer of Pelrin100st, Pelrin 500st series etc. is not to be blend three components and the thermoplastic elastomer that runs through network each other with SEBS, EPDM, PP yet; They generate polymkeric substance by monomer polymerization reactions after generally being employed in and infiltrating monomer, adding initiator, linking agent in the crosslinked rubber (initial network) again; Initial network IPN with cross-linked rubber forms IPN then, or remix carries out polyreaction, makes interpenetrating net polymer (IPN) after processing performed polymer respectively.
Summary of the invention
The purpose of this invention is to provide that a kind of mechanical property is excellent, processing characteristics is better, novel elastic material---the TIEN of broad range of applicability, more environmental protection, low-carbon (LC).
For addressing the above problem, the technical scheme that the present invention adopts is: a kind of commixed type interpenetrating network thermoplastic elastomer TIEN, during production; With SEBS, EPDM, PP is blend three components; And with auxiliary, Synergist S-421 95, linking agent, the weighing in proportion of other auxiliary materials, wherein the weight percent of SEBS is 30～42%, the weight percent of EPDM is 22～36%; The weight percent of PP is 16～22%; The weight percent of auxiliary is 1～2%, and the weight percent of Synergist S-421 95 is 10～16%, and the weight percent of linking agent is 1.2～1.8%; The weight percent of other auxiliary materials is 3%; Segmentation adds respectively in the twin-screw mixer forcing machine behind the mixing, high temperature is molten mix in SEBS at first form IPN with PP, subsequently again with EPDM because of the fine fragment of the chemically crosslinked network of dynamic vulcanization and mechanical shearing generation at two-phase interface layer IPN, form elastomeric interpenetrating(polymer)networks-IEN; The PP crystallization promptly almost is full of whole system, become SEBS/EPDM shared network, make SEBS/EPDM/PP run through network each other to form stable firmly macroscopic view material uniformly.
The invention has the beneficial effects as follows: TPE once was described as the third generation rubber after tree elastomer, viton by people after coming out; Technologies such as it need not vulcanize just can adopt injection, extrude, blowing, mold pressing remove to produce each based article; But traditional TPE; Comprise that with SEBS, EPDM be the TPE that base material makes, exist not enoughly at aspects such as processing forming, goods are apparent that TIEN has improved general T PE (containing TPV) incident disconnected joint, spination and shark skin phenomenon in the extrusion moulding process; The molten current mark that the TPE product surface is prone in the injection molding, depression and other flaws have been alleviated; Improved working accuracy, reduced pair substandard products, especially improved anti-under the severe cold environment (55 ℃) and subdued, twist performance.
TIEN have excellent anti-ozone, anti-weather, ageing-resistant, acid and alkali-resistance, low temperature resistant, resistance to boiling water can, life-time service temperature-60 ℃-125 ℃ is intermittently used to reach 145 ℃; The network structure that TIEN still can be kept perfectly under 250 ℃ of high temperature; Fatigue resistence is remarkable, deflects 100,000 times and does not split, and TIEN does not contain any objectionable impurities; Meet the green instruction of ROHS, thereby broader design space and range of application is provided for the product design slip-stick artist.
Description of drawings
Accompanying drawing 1 is technological process of production figure of the present invention, has shown that intactly the present invention is by the technological process of production of supplementary material to finished product.
Accompanying drawing 2 is morphological structure synoptic diagram of TIEN of the present invention.
In shown in the accompanying drawing 2:
2-1 cell wall (external phase): mainly form by initial network P1 and P3;
2-2 cell space (disperse phase): mainly be made up of the fine fragment of P2 cross-linked network, size is about 0.1-0.3 μ m
The disperse phase that 2-3 is littler: the external phase P1 composition by containing among the P2 constitutes;
The 2-4 fine structure: by the ultrastructure that polymer segment interpenetrates, runs through, tangles and constitute, size is
approximately
2-5 phase interface (interfacial layer): claim zone of transition again, the about 0.01 μ m of thickness is the main region that elastomerics (rubber) P1/P2 network runs through each other, and interfacial layer forms by not exclusively being separated.
Embodiment
The present invention is achieved in that it is main production equipments with the twin-screw mixer forcing machine of specific length-to-diameter ratio (L/D), particular combination module is arranged that TIEN adopts the high speed kneader, is the initial network (hereinafter to be referred as P1) of elastomerics interpenetrating(polymer)networks with SEBS in the blend components; With EPDM is another elastomer network (hereinafter to be referred as P2) of interpenetrating(polymer)networks; Higher with percent crystallinity, the isotatic polypropylene PP of excellent compatibility is all arranged is shared network (hereinafter to be referred as P3) with P1, P2; In the P1/P2/P3 blend components; P1 is as important initial network; Be to constitute the basic condition that elastomerics (rubber) network runs through (IEN) each other, and P3 as shared network (claiming public network) can not only strengthen whole co-mixing system stable stability, prevent to be separated, can also to strengthen the degree of P1/P2 interpenetration network.
During production,, mix the back segmentation and add respectively in the twin-screw mixer forcing machine weighings on demand such as P1, P2, P3 and linking agent, Synergist S-421 95, auxiliarys; Mix in that high temperature is molten, the crystallization of P3 is filled into enough flowabilities in the network of P1 amorphous structure (be that PP crystallization dissolving is scattered in the SEBS amorphous media), forms interpenetrating polymer networks (IPNSEBS/PP) the earliest in the co-mixing system; P2 also forms the chemically crosslinked network by discrete melt because of dynamic vulcanization; And be dispersed among the IPN that P1/P3 forms by the subparticle (network fragment) that the high-shear of machinery is broken for vulcanized rubber; Produce IPN with P1 at two-phase interface layer (claiming zone of transition again); Interfacial layer is that P1/P2 elastomerics (rubber) network runs through the main place of (IEN) each other, and the about 0.01 μ m of the thickness of interpenetrating(polymer)networks is by thermodynamic (al) nonmiscibility and incomplete formation that is separated.
In co-mixing system, the weighting material of the another kind of often elastomerics of elastomerics (rubber) (rubber) that consumption is less is in the actual production; P1 and P2 can have the proportioning scope of broad; P3 and P1, P2 all have good consistency, and the ability high dispersing becomes the shared network of P1/P2 in two kinds of elastomeric networks of difference; Also be the rigidity network in the system, P3 strengthened P1/P2/P3 form one firmly, the ability of stable, macroscopical homogeneous material, the phase farmland size of disperse phase of having reduced.
Identical with most IPN materials; The TIEN that is formed by the P1/P2/P3 interpenetrating(polymer)networks has cellular texture: the more external phase P1 of content is that cell wall, disperse phase P2 are cell space; The about 0.1-0.3 μ of born of the same parents' size m; P1/P2 interpenetrating(polymer)networks zone is on cell space surface (phase interface); In cell space (P2); The composition that also contains cell wall (P1) constitutes littler disperse phase, and the more meticulous structure that still has polymer segment to run through each other, tangle, permeate and form in the external phase (cell wall); Size is approximately about
, fine structure be because the co-mixing system medium viscosity increases and factor such as crosslinked in minimum scope by the secondary generation that is separated.
Owing to adopted such scheme, thereby made a kind of commixed type interpenetrating network thermoplastic elastomer that remarkable mechanical property is arranged: TIEN.
In TIEN; Polymer segment forms the heterogeneous system of the interpenetrating(polymer)networks of a complicacy because of interpenetrating, run through, tangling, except that a part of chemically crosslinked, it is crosslinked with the state of aggregation of segmented copolymer (hard section mutually) to also have that macromolecular entanglement is crosslinked, crystallization is crosslinked; These structures constitute the substruction of TIEN; Also making TIEN have excellent processing characteristics and mechanical property, is that the TIEN test piece of 86A (Shao Shi) is an example with hardness, its tensile strength: >=26mpa, tensile yield: >=630%; Deflecting (antifatigue) does not split for 100,000 times; Through 158 ℃ of * 240h heat ageing test back draft strength retentions be 108%, the tensile yield conservation rate is 95%; Behind the ozone ageing 720h crackle is not arranged; TIEN also has excellent water-fast, anti-steam, chemicals-resistant (acid, alkali, alcohol, ether) performance in addition; Long term operation temperature-60 ℃-125 ℃; Particularly the anti-twist property under processing forming, the low-temperature condition (55 ℃) and apparent SEBS, the EPDM and composition thereof of obviously being superior to of goods also are superior to traditional thermoset rubber and general T PE.
The basic recipe of TIEN is following:
Claims (1)
1. a commixed type interpenetrating network thermoplastic elastomer TIEN during production, is blend three components with SEBS, EPDM, PP; And with auxiliary, Synergist S-421 95, linking agent, the weighing in proportion of other auxiliary materials, wherein the weight percent of SEBS is 30 ~ 42%, the weight percent of EPDM is 22 ~ 36%; The weight percent of PP is 16 ~ 22%; The weight percent of auxiliary is 1 ~ 2%, and the weight percent of Synergist S-421 95 is 10 ~ 16%, and the weight percent of linking agent is 1.2 ~ 1.8%; The weight percent of other auxiliary materials is 3%; Segmentation adds respectively in the twin-screw mixer forcing machine behind the mixing, high temperature is molten mix in SEBS at first form IPN with PP, wear Wang Luo – IEN because of the fine fragment of the dynamic vulcanization and the chemically crosslinked network of mechanical shearing generation at two-phase interface layer IPN, the elastomeric Hu of formation with EPDM again subsequently; The PP crystallization promptly almost is full of whole system, become SEBS/ EPDM shared network, make SEBS/ EPDM/PP run through network each other to form stable firmly macroscopic view material uniformly.
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| CN106317588B (en) * | 2016-08-15 | 2018-07-20 | 福建省二轻工业研究所 | A kind of low temperature resistant, color inhibition thermoplastic elastomer thin film and preparation method thereof |
| CN108997700B (en) * | 2018-09-10 | 2020-06-19 | 福建省二轻工业研究所 | Low-temperature-resistant elastomer resin material suitable for extremely cold regions in polar regions and preparation method thereof |
| CN110982167B (en) * | 2019-12-06 | 2022-07-12 | 万华化学（宁波）有限公司 | Creep-resistant polypropylene composite material with interpenetrating network structure and preparation method thereof |
| CN112126160A (en) * | 2020-09-22 | 2020-12-25 | 江苏金陵奥普特高分子材料有限公司 | TPV (thermoplastic vulcanizate) elastomer for improving normal-temperature compression set and preparation method thereof |
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