CN101781436B - Thermoplastic vulcanized body - Google Patents
Thermoplastic vulcanized body Download PDFInfo
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- CN101781436B CN101781436B CN2009100065024A CN200910006502A CN101781436B CN 101781436 B CN101781436 B CN 101781436B CN 2009100065024 A CN2009100065024 A CN 2009100065024A CN 200910006502 A CN200910006502 A CN 200910006502A CN 101781436 B CN101781436 B CN 101781436B
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Abstract
The invention provides a thermoplastic vulcanized body, which comprises a blend. The blend is formed by dispersing a vulcanized acrylic rubber in a polyester plastic, wherein the vulcanized acrylic rubber is formed by taking an epoxy group-containing resin as a vulcanizing agent and dynamically vulcanizing the acrylic rubber.
Description
Technical field
The present invention relates to a kind of thermoplastic vulcanizates, particularly a kind of thermoplastic vulcanizates through the crosslinked gained of specific vulcanizing agent.
Background technology
Thermoplastic elastomer (Thermoplastic Elastomer, TPE); Be the novel high polymer material that twentieth century develops out mid-term, its have the machine-shaping of conventional plastic quick just, and tool tradition caoutchouc elasticity is good; Advantages such as low compression deformation, hardness are just between traditional rubber-plastic.With traditional hot solidity rubber phase ratio, thermoplastic elastomer (TPE) finished product still can reclaim moulding again, has improved the waste recovery problem of general traditional thermoset rubber, and can reduce the wasting of resources and environmental pollution effectively.Therefore thermoplastic elastomer (TPE) application in these areas has the trend that replaces part rubber gradually, particularly products such as the extruding of high additive value such as steam turbine car spare and accessory parts sports equipment, ejaculation.
In recent years; Thermoplastic vulcanizates (Thermoplastic Vulcanizate, TPV) has become the fastest part of growth in thermoplastic elastomer (TPE) market; Along with scientific and technological demand, the high functional type thermoplastic elastomer of demand under hot environment has the recyclable green material thermoplastic vulcanizates elastomerics that reduces environmental impact that utilizes again concurrently; Bridge formation with similar traditional vulcanized rubber; Make it have preferable resistance against compression and bounce-back property, than the characteristic of the more approaching traditional vulcanized rubber of general thermoplastic elastomer (TPE), so can many-sided replacement parts of traditional thermoset rubber.
Thermoplastic vulcanizates (TPV) consists of the foreign body of plastics and rubber; Mode through dynamic crosslinking is scattered in the continuous base material of plastics sulfuration rubber minuteness particle later; Because propenoate is a soft segment, its main chain is that saturated structures, side group are the polarity ester group, thereby its cross-linked rubber is possessing the elastic while; Have heat-resisting, anti-ozone ageing, oil resistant concurrently, and when burning, do not produce characteristics such as smog and irritant gas.Target is to develop both to have a thermoset vulcanized rubber characteristic, but the thermoplastic elastomer sizing material of thermoplastic shaping again.It has replaced the high-temperature oil resistance sealing member that paracril (NBR) is widely used as automobile, the high-temperature oil resistance cable in the particular surroundings, pipe, band, case and brittle resin plasticized modifier etc. at present.
At present thermoplastic vulcanizates (TPV) technology mainly is that rubber and plastic blends and a specific vulcanizing agent and cocuring agent are carried out dynamic vulcanization is crosslinked, complies with rubber/plastics/vulcanizing agent difference of being selected for use, and obtains tool product of different nature respectively.U.S. Pat 5942577 is to disclose with ACM as the rubber phase in the thermoplastic elastomer; And carrying out vulcanization reaction with amine system (amine cure systems) linking agent, employed plastics are polyester (polyester), polycarbonate (polycarbonate) or polymeric amide (polyamide) mutually; U.S. Pat 6140424 be open with ACM as the rubber phase in the thermoplastic elastomer, linking agent carries out the dynamic vulcanization crosslinking reaction with amine system (amine cure systems) equally, and employed plastics are nylon 6 (Nylon 6) mutually.The thermotolerance of the above-mentioned thermoplastic vulcanizates that prior art obtained has a certain upgrade, but is easy to deliquescence as amine system (the amine cure systems) linking agent of vulcanizing agent, is difficult for preserving.In addition, because use is comparatively expensive than lattice as amine system (amine curesystems) linking agent of vulcanizing agent, the batch process of unfavorable this thermoplastic vulcanizates.Moreover above-mentioned traditional thermoplastic vulcanizates body technique need use tertiary amine (tertiary amine) or MOX, metal hydroxides as cocuring agent, and the essential accurate control of mix proportions between vulcanizing agent and the cocuring agent.
U.S. Pat 5910543 discloses with ACM as the rubber phase in the thermoplastic elastomer; And carrying out the dynamic vulcanization crosslinking reaction as vulcanizing agent with resol (phenolic resin), employed plastics are nylon 6 (Nylon 6) or polybutylene terephthalate (polybutylene terephalate) mutually.The physical strength of the thermoplastic vulcanizates of its gained still needs to improve.
For improving the character of thermoplastic vulcanizates; U.S. Pat 6911103 same with ACM as the rubber phase in the thermoplastic elastomer; Carry out the dynamic vulcanization crosslinking reaction but use sulphur architecture compound (sulfur) instead as vulcanizing agent, employed plastics are polyester (polyester), PS (polystyrene) or polyethylene terephthalate (polyethylene terephthalate) mutually.Compare with U.S. Pat 5910543,, but have relatively poor thermal ageing drag though the thermoplastic vulcanizates of its gained has preferable physical strength.In addition, utilize the mutually high molecular vulcanization rate of sulphur architecture compound (sulfur) dynamic vulcanization cross-linked rubber slow (needing sclerosis for a long time) and more numerous and diverse, therefore prolonged the reaction times, cause than preparation technology's time of length and relatively poor production capacity.
U.S. Pat 6815506 is as the rubber phase in the thermoplastic elastomer with ACM; Carry out the dynamic vulcanization crosslinking reaction but use superoxide (peroxdie) instead as vulcanizing agent, employed plastics are polybutylene terephthalate (polybutylene terephalate) mutually.The thermoplastic vulcanizates of gained has good processibility, but carries out the long setting time of the crosslinked same needs of dynamic vulcanization with superoxide, makes vulcanization rate reduce.In addition, peroxide cross-linking agent is prone to cause molecular degradation.
Therefore, select for use suitable and can improve the vulcanizing agent of sulfuration efficient, improving crosslinking degree, and keep rubber phase and plastics mutually two kinds of polymkeric substance characteristic and simplify preparation technology, the real emphasis that need study for the thermoplastic vulcanizates fabricating technology utmost point.
Summary of the invention
In sum, the present invention proposes a kind of thermoplastic vulcanizates, specifically develops the dynamic crosslinking system to becoming the plastic elastomeric technology of heat, and main purpose is the traditional thermoset rubber of replacement, and goes processing with the thermoplastic processing mode.Preparation technology of the present invention does the dynamic crosslinking technology with curing system; Collocation high length-diameter ratio twin screw extruder is done effective dispersion; Rubber phase is that acryl is rubber (Acrylic rubber, ACM are to be principal monomer with the propenoate); Collocation polyester plastics (polybutylene terephthalate (Polybutylene terephthalate for example; PBT)) as the high workability polyester plastics, and be linking agent with the resin that contains epoxy group(ing) (epoxy), wherein propenoate is the 3 D cross-linked structure of rubber with reticulated structure (network structure) acryl that contains the resin formation of epoxy group(ing); This reticulated structure acryl is that rubber and polyester plastics physical crosslinking microcell interpenetration form two consecutive blends, obtains semi-intercrossing network-thermoplastic vulcanizates (IPN-TPV).This semi-intercrossing network-thermoplastic vulcanizates not only possesses plasticity-, and can keep the primary characteristic of two kinds of polymkeric substance, through improving crosslinking degree, and relatively stable heat-resisting, oil-proofness and effectively reduce compression set property.
Thermoplastic vulcanizates of the present invention; Comprise: a hybrid; Wherein this hybrid is to be that a vulcanized acryl is that to be scattered in a polyester be in the plastics to rubber; Wherein this vulcanized acryl be rubber be with the resin that contains epoxy group(ing) as vulcanizing agent, making acryl is that rubber is via dynamic vulcanization mode gained.
Advantage of the present invention and technical characterictic are; Carry out dynamic vulcanization preparation technology when forming the reticulated structure acryl and being rubber at this acryl resin that is rubber through containing epoxy group(ing) as vulcanizing agent; Need not to use any other non-epoxide resin type vulcanizing agent or also need not to use any cocuring agent (cocuring agent), therefore can omit mix proportions and pan feeding sequential scheduling cumbersome procedure between regulation and control vulcanizing agent and the cocuring agent.In addition; Owing to be to use the resin that contains epoxy group(ing) as vulcanizing agent; This resin that contains epoxy group(ing) is preferably has two or more epoxy group(ing), carries out vulcanization reaction, and its crosslinking degree and vulcanization rate are promoted; Effectively reduce the reaction times, and the thermoplastic vulcanizates of gained has extremely low compression set property (compression set property is less than 1%).
Below through several embodiment and comparing embodiment, illustrating further method of the present invention, characteristic and advantage, but be not to be used for limiting scope of the present invention, scope of the present invention should be benchmark with the appending claims.
Description of drawings
Fig. 1 is sem (SEM) photo for embodiment 1 described novel acrylic ester based thermoplastic elastomerics (A).
Fig. 2 is sem (SEM) photo for the contrast thermoplastic elastomer (A) of comparing embodiment 1 gained.
Fig. 3 is the elongation comparison figure for the prepared thermoplastic elastomer of embodiment 1-3 and comparing embodiment 1-3.
Fig. 4 is embodiment 1,3 and 4-7 and comparing embodiment 1, and the permanent set comparison figure of the prepared thermoplastic elastomer of 3-4.
Embodiment
Thermoplastic vulcanizates of the present invention; Comprise: a hybrid; Wherein this hybrid is to be that a vulcanized acryl is that to be scattered in a polyester be in the plastics to rubber; Wherein this vulcanized acryl be rubber be with the resin that contains epoxy group(ing) as vulcanizing agent, making acryl is that rubber is via dynamic vulcanization mode gained.
In a preferred embodiment; The preparation technology of thermoplastic vulcanizates of the present invention can comprise being that rubber and polyester are the feeding mouth that plastics add twin screw extruder with acryl simultaneously; Employed twin screw extruder can be high length-diameter ratio twin screw extruder (Φ=26; L/D=56); And add contain epoxy group(ing) resin as vulcanizing agent, reaction conditions is controlled at that (the twin screw extruder performance: 120～1200r.p.m), the reaction times can be in 1-10 minute, owing to being to use the resin that contains epoxy group(ing) to carry out the sulfuration of ACM between temperature 200-260 ℃ (deciding according to the rerum natura of rubber and plastic working), screw speed 200-800r.p.m; Can obtain high cross-linking efficiency, can in 2-4 minute, accomplish so generally vulcanize the blending reaction.In addition; In another preferred embodiment of the present invention; This acryl is that rubber can carry out dynamic vulcanization with the resin that contains epoxy group(ing) earlier, and the reticulated structure acryl of gained is that rubber is that plastics utilize the high length-diameter ratio twin screw extruder to do effective dispersion with polyester further again.Above-mentioned preparation technology not only reduces the rapid sulfidation of traditional type multistep, more can effectively improve the preparation technology of time.Thermoplastic elastomer sample after a dynamic crosslinking sulfuration, its elongation (Elongation) is along with degree of crosslinking can effectively promote, and its permanent compression set amount can effectively reduce to below 1%.This is to form two consecutive blends (semi-interpenetrating network polymer (IPN)) because the acryl reticulated structure acryl of gained that is rubber after the epoxy-containing yl resin sulfuration is the physical crosslinking microcell interpenetration of rubber and polyester plastics, reaches fabric of island-in-sea type (island and sea) distributed architecture.The thermoplastic vulcanizates of gained can serve as automobile and electronic component, for example air lead, oil body conduit or car light pad.
This acryl is that rubber can be alkyl acrylate (alkyl acrylate), alkoxy acrylic ester (alkoxy acrylate) or its mixing multipolymer through the polymerization gained; Or tradition is any to can be considered the multipolymer that acryl is rubber (ACM), and wherein this acryl is that the terminal tool of rubber contains reactive functional group (acrylic, acryl or amido) or unsaturated double-bond.
This resin that contains epoxy group(ing) is preferably has two or more epoxy group(ing); Can for example be ortho-cresol type bis-epoxy base (Novolac) type epoxy resin, dihydroxyphenyl propane (bisphenol A) type epoxy resin, cycloaliphatic type (Cyclo aliphatic) epoxy resin or the epoxy resin of bromination (brominated), for example phenolic aldehyde be that ortho-cresol type bifunctional epoxy resin (Phenolic novolac epoxy resin), ortho-cresol phenolic aldehyde are ortho-cresol type bifunctional epoxy resin (cresol novolac epoxy resin), tetrabormated bis phenol-a epoxy resins (Tetrabromobisphenol A diglycidyl ether epoxy), contain naphthalene nucleus epoxy resin (Naphthalene epoxy resin) or two benzyl ring epoxy resins (Diphenylene epoxy resin), two pentamethylene epoxy resin (dicyclopentadiene epoxy resin) or its mixing.This ortho-cresol type bis-epoxy base (Novolac) type epoxy resin can have structure in the present invention's one preferred embodiment:
Wherein R can be hydrogen, alkyl or alkoxyl group, and n >=0, for example is 1,2,3 or 4.
This dihydroxyphenyl propane in the present invention's one preferred embodiment (bisphenol A) type epoxy resin can have structure:
N >=0 wherein.
The epoxy resin of this bromination (brominated) can have structure in the present invention's one preferred embodiment:
N >=0 wherein.
This polyester is that plastics comprise polyethylene terephthalate (polyethylene terephthalate; PET), polybutylene terephthalate (polybutylene terephthalate; PBT), through the poly terephthalic acid hexanaphthene of glycol modification to diformazan alcohol ester (poly (cyclohexylene dimethyleneterephthalate)-Glycol modified polyester; PCTG), polybutylene terephthalate (PBT), through glycol-modified polyethylene terephthalate (poly (ethylene terephthalate)-Glycolmodified polyester; PETG), the poly terephthalic acid hexanaphthene is to diformazan alcohol ester (polycyclohexylenedimethylene terephthalate; PCT), PEN (PEN), PTT (polypropylene terephthalate; PPT) or polytrimethylene terephthalate (polytrimethylene terephthalate, PTT).(this polyester is that plastics are preferably PBT for polybutyleneterephthalate, PBT) plastics tool thermotolerance, good dimension stability, electric property and the good advantage of mechanical properties owing to polybutylene terephthalate.
In the present invention's one preferred embodiment, the acryl that this thermoplastic vulcanizates comprised is that the weight ratio of rubber can be between 10-90wt%, and preferable weight ratio can be that rubber and polyester are that the plastics gross weight is a benchmark with this acryl between 40-60wt%; In the present invention's one preferred embodiment, this polyester that this thermoplastic vulcanizates comprised is that the weight ratio of plastics can be between 10-90wt%, and preferable weight ratio can be that rubber and polyester are that the plastics gross weight is a benchmark with this acryl between 40-60wt%.In addition, this shared weight percent of resin that contains epoxy group(ing) is 1-10wt%, is preferably 2.5-7.5wt%, is that the gross weight of rubber is a benchmark with this acryl.
Below, be to enumerate several embodiment, and ask conjunction with figs., meet acrylic ester thermoplastic elastomer of the present invention with explanation.
The preparation of acrylic ester thermoplastic elastomer
Embodiment 1
Get ethylene-acrylic acid copolymer elastomerics (the ethylene/acrylic elastomer of 100 weight parts; As acryl is rubber) and the polybutylene terephthalate of 100 weight parts (polybutyleneterephthalate, it has following repeating unit: the weight ratio of
therein ethylene-PEMULEN TR2 elastomerics and polybutylene terephthalate is 1: 1.These two kinds of materials are used the single stage method; Utilize high length-diameter ratio twin screw extruder (Φ=26; L/D=56) carry out blend (blending); Add simultaneously ortho-cresol type epoxy group(ing) linking agent (its chemical structure for
n>=0) in twin screw extruder so that the ethylene-acrylic acid copolymer elastomerics is vulcanized, wherein the weight ratio of ortho-cresol type epoxy group(ing) linking agent be 5wt% (with said ethylene-acrylic acid copolymer elastomeric heavy always be benchmark).The operational condition of twin screw extruder is: service temperature is that 220～240 ℃, screw speed are that 500r.p.m, reaction times are 2 minutes, obtains novel acrylic ester based thermoplastic elastomerics (A).Its each ratio of forming is as shown in table 1.Please with reference to Fig. 1, it is the SEM figure of the novel acrylic ester based thermoplastic elastomerics (A) of embodiment 1 (through the epoxy resin sulfuration) gained.
Embodiment 2
Get the ethylene-acrylic acid copolymer elastomerics of 100g and the polybutylene terephthalate of 81.8g, the weight ratio of therein ethylene-PEMULEN TR2 elastomerics and polybutylene terephthalate is 55: 45.These two kinds of materials are used the single stage method; Utilize high length-diameter ratio twin screw extruder (Φ=26; L/D=56) carry out blend; Add simultaneously with embodiment 1 in identical ortho-cresol type epoxy group(ing) linking agent in twin screw extruder so that the ethylene-acrylic acid copolymer elastomerics is vulcanized, wherein the weight ratio of ortho-cresol type epoxy group(ing) linking agent be 5wt% (with this ethylene-acrylic acid copolymer elastomeric heavy always be benchmark).The operational condition of twin screw extruder is: service temperature is that 220～240 ℃, screw speed are that 500r.p.m, reaction times are 2 minutes, obtains novel acrylic ester based thermoplastic elastomerics (B).Its each ratio of forming is as shown in table 1.
Embodiment 3
Get the ethylene-acrylic acid copolymer elastomerics of 100g and the polybutylene terephthalate of 66.7g, the weight ratio of therein ethylene-PEMULEN TR2 elastomerics and polybutylene terephthalate is 60: 40.These two kinds of materials are used the single stage method; Utilize high length-diameter ratio twin screw extruder (Φ=26; L/D=56) carry out blend; Add simultaneously with embodiment 1 in identical ortho-cresol type epoxy group(ing) linking agent in twin screw extruder so that the ethylene-acrylic acid copolymer elastomerics is vulcanized, wherein the weight ratio of ortho-cresol type epoxy group(ing) linking agent be 5wt% (with this ethylene-acrylic acid copolymer elastomeric heavy always be benchmark).The operational condition of twin screw extruder is: service temperature is that 220～240 ℃, screw speed are that 500r.p.m, reaction times are 2 minutes, obtains novel acrylic ester based thermoplastic elastomerics (C).Its each ratio of forming is as shown in table 1.
Embodiment 4
Get the ethylene-acrylic acid copolymer elastomerics of 100g and the polybutylene terephthalate of 150g, the weight ratio of therein ethylene-PEMULEN TR2 elastomerics and polybutylene terephthalate is 40: 60.These two kinds of materials are used the single stage method; Utilize high length-diameter ratio twin screw extruder (Φ=26; L/D=56) carry out blend; Add simultaneously with embodiment 1 in identical ortho-cresol type epoxy group(ing) linking agent in twin screw extruder so that the ethylene-acrylic acid copolymer elastomerics is vulcanized, wherein the weight ratio of ortho-cresol type epoxy group(ing) linking agent be 5wt% (with this ethylene-acrylic acid copolymer elastomeric heavy always be benchmark).The operational condition of twin screw extruder is: service temperature is that 220～240 ℃, screw speed are that 500r.p.m, reaction times are 2 minutes, obtains novel acrylic ester based thermoplastic elastomerics (D).Its each ratio of forming is as shown in table 1.
Embodiment 5
Preparation procedure is with embodiment 1; But wherein the weight ratio of ortho-cresol type epoxy group(ing) linking agent change into 7.5wt% (with this ethylene-acrylic acid copolymer elastomeric heavy always be benchmark); Obtain novel acrylic ester based thermoplastic elastomerics (E), the addition of each composition sees for details shown in the table 1.
Embodiment 6
Preparation procedure is with embodiment 3; But wherein the weight ratio of ortho-cresol type epoxy group(ing) linking agent change into 7.5wt% (with this ethylene-acrylic acid copolymer elastomeric heavy always be benchmark); Obtain novel acrylic ester based thermoplastic elastomerics (F), the addition of each composition sees for details shown in the table 1.
Embodiment 7
Preparation procedure is with embodiment 4; But wherein the weight ratio of ortho-cresol type epoxy group(ing) linking agent change into 7.5wt% (with this ethylene-acrylic acid copolymer elastomeric heavy always be benchmark); Obtain novel acrylic ester based thermoplastic elastomerics (G), the addition of each composition sees for details shown in the table 1.
Comparing embodiment 1
Preparation procedure is with embodiment 1, but do not add said ortho-cresol type epoxy group(ing) linking agent fully in this twin screw extruder (promptly ACM not being vulcanized), obtains contrasting thermoplastic elastomer (A), and the addition of each composition sees for details shown in the table 1.Please with reference to Fig. 2, it is the SEM figure of the contrast thermoplastic elastomer (A) of comparing embodiment 1 gained.
Whether Fig. 1 and thermoplastic elastomer difference shown in Figure 2 are to utilize epoxy resin to vulcanize; Can know by Fig. 1 and Fig. 2; When ACM/PBT behind the epoxy resin dynamic vulcanization, rubber phase (soft segment) can more be uniformly distributed in plastics mutually in (hard segment).
Comparing embodiment 2
Preparation procedure is with embodiment 2, but do not add said ortho-cresol type epoxy group(ing) linking agent fully in this twin screw extruder (promptly ACM not being vulcanized), obtains contrasting thermoplastic elastomer (B), and the addition of each composition sees for details shown in the table 1.
Comparing embodiment 3
Preparation procedure is with embodiment 3, but do not add said ortho-cresol type epoxy group(ing) linking agent fully in this twin screw extruder (promptly ACM not being vulcanized), obtains contrasting thermoplastic elastomer (C), and the addition of each composition sees for details shown in the table 1.
Comparing embodiment 4
Preparation procedure is with embodiment 4, but do not add said ortho-cresol type epoxy group(ing) linking agent fully in this twin screw extruder (promptly ACM not being vulcanized), obtains contrasting thermoplastic elastomer (D), and the addition of each composition sees for details shown in the table 1.
Table 1
| The embodiment numbering | Ethylene-acrylic acid copolymer elastomerics (ACM) | Polybutylene terephthalate (PBT) | The wt ratio of ACM/PBT | The weight ratio of ortho-cresol type epoxy group(ing) linking agent | |
| Embodiment 1 | | 100g | 50∶50 | 5wt％ | |
| Embodiment 2 | 100g | 81.8g | 55∶45 | 5wt％ | |
| Embodiment 3 | 100g | 66.7 |
60∶40 | 5wt％ | |
| Embodiment 4 | | 150g | 40∶60 | 5wt％ | |
| Embodiment 5 | 100g | 100g | 50∶50 | 7.5wt％ | |
| Embodiment 6 | 100g | 66.7 |
60∶40 | 7.5wt％ | |
| Embodiment 7 | 100g | 150g | 40∶60 | 7.5wt％ | |
| Comparing embodiment 1 | 100g | 100g | 50∶50 | 0 | |
| Comparing embodiment 2 | 100g | 81.8g | 55∶45 | 0 | |
| Comparing embodiment 3 | 100g | 66.7 |
60∶40 | 0 |
The thermoplastic elastic volume property is measured
Embodiment 8
Thermoplastic elastomer with embodiment 1, embodiment 2, embodiment 3, comparing embodiment 1, comparing embodiment 2 and comparing embodiment 3 gained carries out surface hardness (shore hardness, ShoreHardness D respectively; Testing method according to ASTM D-2240 defined), elongation (elongation; Testing method according to ASTM D-412 defined; Rate of extension 500%) and the compression set rate (Compression Set (Cs), according to the testing method of ASTM D-395 defined; Survey formula condition is: 100 ℃, 24hr, compression test piece 25%), it is as shown in table 2 to survey the formula result.
Table 2
| Surface hardness (Shore D) | Elongation (%) | Compression set rate (%) | |
| Embodiment 1 | 36 | 198.9 | 0.03 |
| Embodiment 2 | 23 | 222.3 | 0.21 |
| Embodiment 3 | 22 | 268.89 | 0.23 |
| Comparing embodiment 1 | 29 | 139.41 | 44.28 |
| Comparing embodiment 2 | 17 | 113.88 | 18.13 |
| Comparing embodiment 3 | 10 | 112.6 | 86.4 |
Please with reference to Fig. 3; It is presented under the identical ACM/PBT ratio, and the contrast of adding ortho-cresol type epoxy group(ing) linking agent and the elongation (elongation) of the thermoplastic elastomer that does not have interpolation ortho-cresol type epoxy group(ing) linking agent gained (be embodiment 1 compares with comparing embodiment 1, embodiment 2 compares with comparing embodiment 2, embodiment 3 compare with comparing embodiment 3) is arranged; In addition; Please with reference to Fig. 4; It is presented under the identical ACM/PBT ratio, the contrast of different ortho-cresol type epoxy group(ing) linking agent additions and the compression set rate of the thermoplastic elastomer that do not have to add ortho-cresol type epoxy group(ing) linking agent gained (be that embodiment 1, embodiment 5 compare with comparing embodiment 1, embodiment 3, embodiment 6 compare with comparing embodiment 3, embodiment 4, embodiment 7 compare with comparing embodiment 4).Can know that by table 2 and Fig. 3 after after adding the epoxy group(ing) linking agent, vulcanizing, the elongation of the thermoplastic elastomer of gained obviously increases; In addition; Can know by table 2 and Fig. 4; Carry out the sulfuration of thermoplastic elastomer behind the embodiments of the invention use epoxy group(ing) linking agent, can significantly improve the compression set rate of thermoplastic elastomer, the compression set rate of the thermoplastic elastomer after the sulfuration of gained is all less than 1%.
Though the present invention with preferred embodiment openly as above; Right its is not in order to limit the present invention; Any those skilled in the art; Do not breaking away from the spirit and scope of the present invention, when can doing a little change and retouching, so protection scope of the present invention is benchmark when looking the person of defining of accompanying Claim book institute.
Claims (23)
1. thermoplastic vulcanizates, it is to be obtained by following preparation technology:
Be that rubber and polyester are the feeding mouth that plastics add twin screw extruder with acryl simultaneously; Employed twin screw extruder is that high length-diameter ratio twin screw extruder and the performance of Φ=26, L/D=56 is 120～1200r.p.m; And add contain epoxy group(ing) resin as vulcanizing agent, reaction conditions is controlled between temperature 200-260 ℃, screw speed 200-800r.p.m, the reaction times is in 1-10 minute;
The compression set property of the thermoplastic vulcanizates of gained is less than 1%.
2. thermoplastic vulcanizates according to claim 1, the weight ratio that wherein said vulcanized acryl is a rubber are that rubber and polyester are that the plastics gross weight is a benchmark between 10-90wt% with said acryl.
3. thermoplastic vulcanizates according to claim 1, wherein said acryl be the weight ratio of rubber between 40-60wt%, be that rubber and polyester are that the plastics gross weight is a benchmark with said acryl.
4. thermoplastic vulcanizates according to claim 1; Wherein said polyester is that plastics are polybutylene terephthalate; The weight ratio of said polybutylene terephthalate is that rubber and polyester are that the plastics gross weight is a benchmark between 10-90wt% with said acryl.
5. thermoplastic vulcanizates according to claim 1; Wherein said polyester is that plastics are polybutylene terephthalate; The weight ratio of said polyphenyl dioctyl phthalate butanediol ester is that rubber and polyester are that the plastics gross weight is a benchmark between 40-60wt% with said acryl.
6. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) has two or more epoxy group(ing).
7. thermoplastic vulcanizates according to claim 1, wherein said vulcanized acryl is that rubber has reticulated structure.
8. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) are ortho-cresol type bis-epoxy fundamental mode epoxy resin (Novolac epoxy resin).
9. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) are that phenolic aldehyde is ortho-cresol type bifunctional epoxy resin (Phenolic novolac epoxy resin).
10. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) is ortho-cresol type bifunctional epoxy resin (cresol novolac epoxy resin) for the ortho-cresol phenolic aldehyde.
11. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) is a bisphenol A type epoxy resin.
12. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) be the tetrabormated bis phenol-a epoxy resins, contain naphthalene nucleus epoxy resin or two benzyl ring epoxy resins.
13. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) is a cycloaliphatic type epoxy resin.
14. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) is two pentamethylene epoxy resin.
15. thermoplastic vulcanizates according to claim 1, the wherein said resin that contains epoxy group(ing) is the epoxy resin of bromination.
16. thermoplastic vulcanizates according to claim 1, the wherein said shared weight percent of resin that contains epoxy group(ing) is 1-10wt%, is that the gross weight of rubber is a benchmark with said acryl.
17. thermoplastic vulcanizates according to claim 1, the wherein said shared weight percent of resin that contains epoxy group(ing) is 2.5-7.5wt%, is that the gross weight of rubber is a benchmark with said acryl.
18. thermoplastic vulcanizates according to claim 1, wherein said acryl are rubber when carrying out dynamic vulcanization preparation technology through the resin that contains epoxy group(ing) as vulcanizing agent, need not to use cocuring agent.
19. thermoplastic vulcanizates according to claim 1, wherein said acryl are rubber is alkyl acrylate, alkoxy acrylic ester or its mixing multipolymer through the polymerization gained.
20. thermoplastic vulcanizates according to claim 1, wherein said polyester are plastics be polyethylene terephthalate, polybutylene terephthalate, through the poly terephthalic acid hexanaphthene of glycol modification to the diformazan alcohol ester, through glycol-modified polyethylene terephthalate, poly terephthalic acid hexanaphthene to diformazan alcohol ester, PEN or PTT.
21. thermoplastic vulcanizates according to claim 1, wherein said thermoplastic vulcanizates has half interpenetrating network structure.
22. thermoplastic vulcanizates according to claim 1, wherein said thermoplastic vulcanizates are to be applied to automobile and electronic component.
23. thermoplastic vulcanizates according to claim 1, wherein said thermoplastic vulcanizates are as air lead, oil body conduit or car light pad.
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| CN2009100065024A CN101781436B (en) | 2009-01-21 | 2009-01-21 | Thermoplastic vulcanized body |
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| CN2009100065024A CN101781436B (en) | 2009-01-21 | 2009-01-21 | Thermoplastic vulcanized body |
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| CN101781436B true CN101781436B (en) | 2012-08-15 |
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| CN2009100065024A Active CN101781436B (en) | 2009-01-21 | 2009-01-21 | Thermoplastic vulcanized body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020201294A1 (en) * | 2019-04-03 | 2020-10-08 | Hutchinson | Thermoplastic elastomer composition for a motor vehicle pipe, method for preparing same, flexible component and air circuit incorporating same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102585416A (en) * | 2012-03-13 | 2012-07-18 | 北京化工大学 | High-temperature-resistant oil-proof thermoplastic vulcanizate (TPV) |
| TWI704179B (en) * | 2018-12-07 | 2020-09-11 | 財團法人工業技術研究院 | Thermoplastic vulcanizate and manufacturing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020201294A1 (en) * | 2019-04-03 | 2020-10-08 | Hutchinson | Thermoplastic elastomer composition for a motor vehicle pipe, method for preparing same, flexible component and air circuit incorporating same |
| FR3094720A1 (en) * | 2019-04-03 | 2020-10-09 | Hutchinson | Thermoplastic elastomer composition for motor vehicle ducts, its preparation process, flexible part and air circuit incorporating it |
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