CN101983990B - Thermoplastic elastomer and preparation method thereof - Google Patents

Abstract

The invention discloses a thermoplastic elastomer and a preparation method thereof. The thermoplastic elastomer comprises the following components in parts by weight: 20-70 parts of oil charge hydrogenated styrene resin, 20-80 parts of strong-polarity polymer resin, 6-25 parts of compatilizer, 1-19 parts of processing aid and 1-4 parts of weatherproof agent. On the basis of satisfying the usability of TPE material, the invention obtains ideal processing flowability and totally can shape film-wall workpieces by screening and matching the oil charge hydrogenated styrene resin, the strong-polarity polymer resin, the efficient compatilizer, efficient weatherproof agent and various processing aids. The produced FLEXBOND series product has the following advantages: (1) multiple cladding: acrylonitrile butadiene styrene acrylonitrile butadiene styrene (ABS), polycarbonate (PC)/ABS, PC, polyacetal (POM) and polybutylece terephthalate (PBT) are coated and shaped under different processing conditions; (2) excellent physical and mechanical properties; (3) good weather resistance: the product can satisfy the storage and use requirements of products; (4) good material flowability and easy shaping, and capability of satisfying precise shaping requirements; and (5) capability of conforming to the environmentally-friendly requirement.

Description

A kind of thermoplastic elastomer and preparation method thereof

Technical field

The present invention relates to a kind of thermoplastic elastomer.

Background technology

Thermoplastic elastomer (TPE, Thermoplastic Elastomer) is claimed TPR (TPE again; Thermoplastic Rubber), be novel elastomer, it has experienced four developmental stage (1985～1967; 1968～1977,1989～the present), obtained long-run development; Emerge many industrialization products, become and the strong rival of traditional vulcanized rubber.China's rapid economy development has driven the development of industries such as automobile, building, electric wire, the consumer's goods in recent years, and the market requirement of thermoplastic elastomer product is also in continuous growth.Along with thermoplastic elastomer is classified as country's " 863 Program ", support project, the market development prospect is more and more wide.

Thermoplastic elastomer (TPE) material has advantage recyclable, in light weight, that rebound resilience is high, sense of touch is good, thereby is applied to high-end power tool, electronic apparatus, electric wire, instrument, medicine equipment and other field more and more.Thermoplastic elastomer (TPE) material is applied to Overmoldedly being seen everywhere building implement class such as nailing machine, electric drill etc. in daily life; Daily life tools class such as suction cleaner, toothbrush, scissors handle etc.; Kitchen utensils class such as dishwasher, refrigerator sealed strip etc.; Sports goods class such as ball handle, swimming sealed mirror etc.; Current consumption article such as shoes, hundle-bar or the like.Because the continuous expansion of thermoplastic elastomer (TPE) material Application Areas; Since the nineties in last century; Thermoplastic elastomer (TPE) material at full speed increases always, and along with the atrophy in flexible PVC market, thermoplastic elastomer (TPE) material prospect is more good by market.

At present; Main thermoplastic elastomer (TPE) material on the market, major part be by U.S. GLS, mountain all put down, international corporations such as Polyone and German glue treasured manufacture, and review domestic; Although the producer of domestic production thermoplastic elastomer (TPE) material has a lot; But all concentrate on low and middle-end TPE development of market mostly, high-end Overmolded with TPE and more high-end TPV, TPSiv etc. like PA, POM, the domestic enterprise that sets foot in still is fewer.

One aspect of the present invention is to the design and the optimization of oil-filled hydrogenated styrene resinoid, strong polar fluoropolymer resin, efficient compatilizer, efficient weather resisting agent and various processing aids; On the other hand through back independent developments such as research screw-type, length-to-diameter ratios special screwing element and combination and various support equipment; Form the special-purpose twin screw extruder group of unique thermoplastic elastomer (TPE) material; Compare with the common double screw extrusion press; This improves online oil-filled continuity and plastic, rubber biphase homogenizing consistency that unit has been taken into account the hydrogenated styrene resinoid; Preparation realizes that thermoplastic elastomer (TPE) material coats the overall equilbrium between use properties and processing characteristics; And realize Overmolded to different resins matrixes such as ABS, PC/ABS, PC, POM, PBT with a kind of thermoplastic elastomer (TPE) material through the adjusting process parameter, promoted the state of the art of China's thermoplastic elastomer (TPE) material on the part degree.

Summary of the invention

The objective of the invention is to fundamentally solve the problem that purposes thermoplastic elastomer (TPE) material coating use properties is difficult to take into account simultaneously different matrix such as ABS, PC/ABS, PC, POM, PBT that coats; Under the prerequisite of physical and mechanical properties excellence, improve performances such as product flowability, weathering resistance.Prepare a kind of thermoplastic elastomer that can coat simultaneously different resins body materials such as ABS, PC/ABS, PC, POM, PBT.

Another object of the present invention provides above-mentioned process for preparation of thermoplastic elastomer.

Thermoplastic elastomer of the present invention comprises the component of following parts by weight:

Oil-filled hydrogenated styrene resinoid 20-70 part

Strong polar fluoropolymer resin 20-80 part

Compatilizer 6-25 part

Processing aid 1-19 part

Weather resisting agent 1-4 part.

In above-mentioned thermoplastic elastomer, can also add other auxiliary agents 1-8 part.

In above-mentioned thermoplastic elastomer; Described oil-filled hydrogenated styrene resinoid is to form by possessing different mobile hydrogenated styrene mixed with resin; Wherein the hydrogenated styrene resin of high workability is to be that the hydrogenated styrene resin of 10-25 ten thousand constitutes by molecular weight, and high mobile hydrogenated styrene resin accounts for 30-65 weight %.

In above-mentioned thermoplastic elastomer, described strong polar fluoropolymer resin is meant and ABS, PC/ABS, PC, POM, PBT resin affinity better polymerization resin.

In above-mentioned thermoplastic elastomer, described compatilizer is preferably the maleic anhydride graft styrene resin, like SEBS-MAH, SBS-MAH etc.

In above-mentioned thermoplastic elastomer, described weather resisting agent is that UV-P is the weather-proof system on basis.

In above-mentioned thermoplastic elastomer, described processing aid is preferably mineral oils, modified silicone resin,-vinyl toluene oligopolymer or erucic acid acyl ammonia.

Above-mentioned process for preparation of thermoplastic elastomer comprises following two steps:

(1) adds oil-filled hydrogenated styrene resinoid, compatilizer, strong polar fluoropolymer resin, processing aid, weather resisting agent, other auxiliary agents successively, in high-speed mixer, carry out the mixing of 7-10min under 40-80 ℃ of condition.

(2) above-mentioned mixing material is mixed granulation through counter rotation twin screw extruder.

Compared with prior art, the present invention has following beneficial effect:

Thermoplastic elastomer of the present invention be by the oil-filled hydrogenated styrene analog compound resin of the good high workability characteristics of consistency with possess the blend of strong polar polymkeric substance compound resin and form.As everyone knows, the quality of intermingling material mechanical property depends on the consistency of co-mixing system to a great extent.If co-mixing system two is alternate incompatible, the macromole between the phase repels each other fully, and each polymeric constituent flocks together alone, forms phase separation structure, certainly will stay vulnerable area at material internal, and the mechanical property of material must variation.If co-mixing system is compatible fully, two kinds of macromole realize that molecular levels disperse, its performance also can only be two components simply adding with, and do not have significant improvement.These two kinds of extreme cases, promptly two is fully incompatible or compatible fully mutually, all not ideal enough concerning a co-mixing system, inaccessible improved purpose.Our desirable co-mixing system is between compatible and incompatible fully, and promptly half-phase holds state (or claiming that part is compatible), makes co-mixing system when guaranteeing to form rubber toughened disperse phase, and two have good cohesive force again between mutually.Therefore, whether the TPE material of Overmolded usefulness has use value, and two alternate consistencies are primary factor.Microcosmic means such as macroscopical means such as the mechanical property of the present invention through test TPE material, weld bond intensity and DSC, SEM pattern photo; Show that selected compatilizer both had good consistency with oil-filled hydrogenated styrene analog; With strong polar polymkeric substance compound resin good consistency is arranged again; Thereby impel interpenetrating and spreading of macromolecular chain segment, improve the cohesive force between the phase interface.

Secondly through research and development, give TPE material better weather ability to weather-proof system.The present invention is through the research of strong polar polymkeric substance compound resin kind and consumption; Apolegamy is the weather-proof system on basis with the good UV-P of system consistency; Can realize xenon lamp test 1000 hours, Δ E (1000h) is still less than 2, and institute's development goods have use in African market.

Once more, because the TPE material is the co-mixing system that tack of materials and elasticity are had relatively high expectations, so the flowability of TPE material is the individual problem points that can't avoid in the TPE developing material.The present invention studies the flowability of improving the TPE material, has selected the most effectively processing aid mineral oils, organically-modified silicone resin and a-Methylstyrene Low-Polymer etc. for use.

The present invention is through the screening and the collocation of oil-filled hydrogenated styrene resinoid, strong polar fluoropolymer resin, efficient compatilizer, efficient weather resisting agent and various processing aids; Satisfying on the TPE material use properties basis; Obtain the ideal processing fluidity, moulding that fully can thin wall parts.The FLEXBOND series product of being produced have: 1. purposes that coat, different processing conditionss can realize Overmolded to ABS, PC/ABS, PC, POM, PBT down more; 2. excellent physical and mechanical performance; 3. weather resistance is good, can satisfy the requirement in product storage and the use; 4. material flowability is good, and easy-formation can satisfy the precise forming requirement; 5. compliance with environmental protection requirements.

Embodiment:

Embodiment 1 (preparation of FLEXBOND-1026BFENC001 product)

Get 40 parts of SEBS resins, 45 parts of TPU resins, 12 parts of SEBS-MAH, 5 parts of SMA, UV-P2 part, 2 parts of other auxiliary agents.Add SEBS resin, SEBS-MAH, TPU resin, SMA, UV-P, other auxiliary agents then successively, in high-speed mixer, carry out the mixing of 10min under 50 ℃ of conditions, then through the counter rotation twin screw extruder granulation.Resulting material gained performance is as shown in table 1.

Table 1 FLEXBOND-1026BFE NC001 product performance

Embodiment 2 (preparation of FLEXBOND-1028AFE NC004 product)

Get 30 parts of SBS resins, 65 parts of TPA resins, 10 parts of SBS-MAH, 7 parts of SMA, 1.5 parts of UV-P, 3 parts of other auxiliary agents.Add SBS resin, SBS-MAH, TPA resin, SMA, UV-P, other auxiliary agents then successively, in high-speed mixer, carry out the mixing of 7min under 70 ℃ of conditions, then through the counter rotation twin screw extruder granulation.Resulting material gained performance is as shown in table 1.

Table 1 FLEXBOND-1028AFE NC004 product performance

Can find out that from product performance the FLEXBOND series product of production have the purposes that coat more, excellent physical and mechanical performance and weather resistance have the extremely strong market competitiveness.

Claims (6)

1. thermoplastic elastomer is characterized in that comprising the component of following parts by weight:

Described oil-filled hydrogenated styrene resinoid is to form by possessing different mobile hydrogenated styrene mixed with resin; Wherein the hydrogenated styrene resin of high workability is to be that the hydrogenated styrene resin of 10-25 ten thousand constitutes by molecular weight, and high mobile hydrogenated styrene resin accounts for 30-65 weight %;

Described strong polar fluoropolymer resin is the TPUE resin.

2. thermoplastic elastomer as claimed in claim 1 is characterized in that, also contains other auxiliary agents 1-8 part.

3. thermoplastic elastomer as claimed in claim 1 is characterized in that, described compatilizer is the maleic anhydride graft styrene resin.

4. thermoplastic elastomer as claimed in claim 1 is characterized in that, described weather resisting agent is that UV-P is the weather-proof system on basis.

5. thermoplastic elastomer as claimed in claim 1 is characterized in that, described processing aid is mineral oils, modified silicone resin or erucic acid acyl ammonia.

6. the said process for preparation of thermoplastic elastomer of claim 1 is characterized in that comprising following steps:

(1) adds oil-filled hydrogenated styrene resinoid, compatilizer, strong polar fluoropolymer resin, processing aid, weather resisting agent, other auxiliary agents successively, in high-speed mixer, carry out the mixing of 7-10min under 40-80 ℃ of condition;

(2) above-mentioned mixing material is mixed granulation through counter rotation twin screw extruder.