Technology contents
The technical problems to be solved in the utility model is to provide a kind of method for preparing dynamic vulcanization thermoplastic elastomer, so that prepare the dynamic vulcanization thermoplastic elastomer of high workability, low compression set, soft, improve its equipment scope of application, production efficiency and reduce production costs.
The method for preparing thermoplastic elastomer through dynamic vulcanization that the present invention proposes is as follows:
(1) preparation of a reactive step material: part rubber, plastics, filler, tenderizer, aging agent and processing aid are carried out the melt blending granulation, and wherein rubber accounts for the 10-70% of rubber gross weight in the prepared thermoplastic elastomer;
(2) preparation of vulcanizing agent rubber master batch: with vulcanizing agent and the granulation of part blend rubber, wherein rubber accounts for the 20-60% of rubber gross weight in the prepared thermoplastic elastomer;
(3) preparation of promotor rubber master batch: with promotor and the granulation of part blend rubber, wherein promotor accounts for the 5-30% of rubber gross weight in the prepared thermoplastic elastomer;
(4) dynamic vulcanization: one step of reactivity material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three steps preparation are mixed into the sulfuration of action attitude.
Except that vulcanizing agent rubber master batch and promotor rubber master batch, prescription used in the present invention is the prescription of the dynamic vulcanization thermoplastic elastomer of routine, and the raw material that uses is the known raw material that can be used for dynamic vulcanization thermoplastic elastomer.Wherein rubber can be selected chloroprene rubber, natural rubber, trans-isoprene, terpolymer EP rubber, cis-1,4-polybutadiene rubber, ethylene-vinyl acetate copolymer, chlorinated polyethylene rubber, acrylic elastomer, paracril, styrene-butadiene rubber(SBR) or their mixture; Plastics comprise polyethylene, polystyrene, polyvinyl chloride, polypropylene, polymeric amide, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polycarbonate, polymethylmethacrylate, polybutylene terephthalate or their mixture; Filler has white carbon black, carbon black, lime carbonate, talcum powder, potter's clay; Tenderizer comprises naphthenic oil, paraffin oil, white mineral oil, Vaseline; Aging agent comprises 1010 (Hinered phenols), 168 (phosphorous acid esters); Processing aid comprises stearic acid, polyethylene wax.
Described vulcanizing agent comprises organo-peroxide, sulphur, resol, brominated phenolic resin or their mixture.
Vulcanizing agent component concentration per-cent in the vulcanizing agent rubber master batch is 5-90%, wherein preferred 20-80%.
Described promotor comprises dithiocarbamate(s), xanthogenic acid salt, thiazole salt, Thiourea, guanidine class, sulfenamide, thiurams, aldehyde amines, metal halide class or their mixture, wherein preferred ziram, zinc n butylxanthate, dibenzothiazyl disulfide, thiocarbamyl sulfenamide, vulkacit D, bad hexyl of N--2-[4-morpholinodithio sulphenamide, tetramethyl-thiuram disulfide, hexamethylenetetramine or 2-benzothiazolyl mercaptan.
Promoter component percentage composition in the promotor rubber master batch is 2-85%, wherein preferred 10-80%.
In formula system, the usage quantity of vulcanizing agent is fewer, therefore direct adding then is difficult in the system and mixes, cause the rubber phase state of vulcanization inequality in the system easily, part rubber phase over cure, and another part rubber phase is undervulcanization, makes that prepared dynamic vulcanization thermoplastic elastomer quality is inhomogeneous; Same, because the promotor usage quantity is seldom, directly adding is difficult in the system and mixes, and causes the rubber phase vulcanization rate difference in the system easily.
Vulcanizing agent and part rubber are prepared into the vulcanizing agent rubber master batch, owing to do not have promotor in the vulcanizing agent rubber master batch, and temperature is a normal temperature during preparation vulcanizing agent rubber master batch, therefore can avoid vulcanizing agent and rubber phase generation prevulcanized, as previously mentioned, vulcanizing agent rubber master batch and promotor rubber master batch are joined after the system, along with beginning of shearing carries out, vulcanizing agent rubber master batch and promotor rubber master batch begin to disperse in a reactive step material, vulcanizing agent contacts with promotor beginning and carries out vulcanization reaction with rubber phase simultaneously, because employing vulcanizing agent and promotor are adopted the mode of rubber master batch rather than directly added, thereby more even with contacting of rubber phase, thereby improve the uniformity coefficient of its sulfidation.Equally, vulcanizing agent and promotor contact with rubber gradually along with the carrying out of shearing and carry out vulcanization reaction, thereby the danger of having avoided the rubber phase overcuring and can not having continued to be sheared, and the easier island structure that is sheared into certain fineness of rubber phase is dispersed in the plastic substrate.
Of the present invention pair of rubber master batch legal system is equipped with the method for thermoplastic elastomer, and its advantage is as follows:
Owing to adopt the mode of rubber master batch rather than directly add vulcanizing agent and promotor, thereby it is more even with contacting of rubber phase, thereby improve the uniformity coefficient of its sulfidation, equally, vulcanizing agent and promotor contact with rubber gradually along with the carrying out of shearing and carry out vulcanization reaction, thereby have avoided the problem that excessively causes rubber phase to be difficult to shear because of prevulcanized.
Use the promotor rubber master batch to make usage quantity promotor seldom easier mixing in system, on the other hand, after promotor is scattered in rubber master batch, no dust, pollution-free, be suitable for automatic weighing operation, for the processing of dynamic vulcanization thermoplastic elastomer brings convenience.
In a word, the rubber that adopts two rubber master batch technology to solve disperse phase should tight cure has the difficult point of certain fineness again, and prepared dynamic vulcanization thermoplastic elastomer has advantages such as high workability, low compression set, soft, and quality is more even.And, adopt two rubber master batch technology to associate velocity of shear and vulcanization rate, thereby reduce dependency equipment and technology, have equipment and be suitable for advantages such as wide, that preparation technology is simple, process window is wide.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but the present invention is confined to scope of embodiments.
In following embodiment, aging agent can be selected 1010 (Hinered phenols) or 168 (phosphorous acid esters) for use, and processing aid comprises stearic acid or polyethylene wax.
Embodiment 1
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 30 parts of terpolymer EP rubbers (EPDM), 40 parts of polypropylene (PP), 10 parts of filler white carbon blacks, 30 parts of tenderizer white mineral oils, 0.5 part of aging agent, 0.5 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 3 parts of vulcanizing agent resol and 20 parts of EPDM are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 0.6 part of promotor ziram and 10 parts of EPDM are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank cocurrent and parallel twin screw extruder and obtain rubber and plastic than EPT rubber (EPDM/PP) dynamic vulcanization thermoplastic elastomer that is 60/40.
Embodiment 2
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 40 parts of paracrils (NBR), 30 parts of polyamide (PA)s, 5 parts of filler carbon blacks, 10 parts of tenderizer Vaseline, 0.4 part of aging agent, 0.6 part of processing aid are mixed in 200 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 4 parts of vulcanizing agent sulphur and 20 parts of NBR are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 0.7 part of promotor zinc n butylxanthate and 10 parts of NBR are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 200 ℃ the mixing tank and obtain rubber and plastic than paracril/polymeric amide (NBR/PA) dynamic vulcanization thermoplastic elastomer that is 70/30.
Embodiment 3
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 10 parts of chloroprene rubbers (CR), 40 parts of polyethylene (PE), 25 parts of filler-calcium carbonates, 24 parts of tenderizer naphthenic oils, 0.5 part of aging agent, 0.5 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 6 parts of vulcanizing agent brominated phenolic resins and 60 parts of chloroprene rubbers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 0.7 part of accelerator dibenzothiazyl disulfide and 30 parts of chloroprene rubbers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank and obtain rubber and plastic than the chloroprene rubber/polyethylene that is 100/40
(CR/PE) dynamic vulcanization thermoplastic elastomer.
Embodiment 4
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 20 parts of trans-isoprenes (TPI), 40 parts of polystyrene (PS), 20 parts of filler talcum powder, 25 parts of tenderizer Vaseline, 0.5 part of aging agent, 0.5 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 8 parts of vulcanizing agent sulphur and 12 parts of trans-isoprenes are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 1.2 parts of promotor thiocarbamyl sulfenamides and 8 parts of trans-isoprenes are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank and obtain rubber and plastic than trans-isoprene/polystyrene (TPI/PS) dynamic vulcanization thermoplastic elastomer that is 40/40.
Embodiment 5
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 35 parts of cis-1,4-polybutadiene rubbers (BR), 40 parts of polyvinyl chloride (PVC), 10 parts of filler potter's clay, 30 parts of tenderizer paraffin oils, 0.4 part of aging agent, 0.8 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 9 parts of vulcanizing agent benzoyl peroxides and 1 part of cis-1,4-polybutadiene rubber are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 6 parts of promotor vulkacit D and 14 parts of cis-1,4-polybutadiene rubbers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank and obtain rubber and plastic than cis-1,4-polybutadiene rubber/vinylchlorid (BR/PVC) dynamic vulcanization thermoplastic elastomer that is 50/40.
Embodiment 6
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 40 parts of ethylene-vinyl acetate copolymers (EVA), 40 parts of polycarbonate (PC), 10 parts of filler-calcium carbonates, 35 parts of tenderizer naphthenic oils, 0.8 part of aging agent, 0.6 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 10 parts of vulcanizing agent resol and 13.5 parts of ethylene-vinyl acetate copolymers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 8.5 parts of accelerant N-cyclohexyl-2-[4-morpholinodithio sulphenamide and 1.5 parts of ethylene-vinyl acetate copolymers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank and obtain rubber and plastic than ethylene-vinyl acetate copolymer/polycarbonate (EVA/PC) dynamic vulcanization thermoplastic elastomer that is 55/40.
Embodiment 7
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 60 parts of chlorinated polyethylene rubbers (CM), 20 parts of polymethylmethacrylates (PMMA), 9 parts of filler carbon blacks, 30 parts of tenderizer paraffin oils, 0.7 part of aging agent, 0.4 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 0.3 part of vulcanizing agent sulphur and 15 parts of chlorinated polyethylene rubbers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 2 parts of accelerant disulfide tetra methylthiurams and 10 parts of chlorinated polyethylene rubbers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank and obtain rubber and plastic than chlorinated polyethylene rubber/polymethylmethacrylate (CM/PMMA) dynamic vulcanization thermoplastic elastomer that is 85/40.
Embodiment 8
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 40 parts of acrylic elastomers (ACM), 40 parts of polybutylene terephthalates (PBT), 10 parts of filler white carbon blacks, 26 parts of tenderizer Vaseline, 0.7 part of aging agent, 0.5 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 3 parts of vulcanizing agent resol and 22 parts of acrylic elastomers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 2 parts of promotor hexamethylenetetramines and 8 parts of acrylic elastomers are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank and obtain rubber and plastic than acrylic elastomer/polybutylene terephthalate (ACM/PBT) dynamic vulcanization thermoplastic elastomer that is 70/40.
Embodiment 9
A kind of method for preparing thermoplastic elastomer through dynamic vulcanization, step is as follows:
1) preparation of a reactive step material: 30 parts of styrene-butadiene rubber(SBR) (SBR), 30 parts of acrylonitrile-butadiene-styrene copolymers (ABS), 10 parts of filler talcum powder, 22 parts of tenderizer white mineral oils, 0.5 part of aging agent, 0.7 part of processing aid are mixed in 180 ℃ of mixing tanks, carry out granulation then, obtain a reactive step material.
2) preparation of vulcanizing agent rubber master batch: 5 parts of vulcanizing agent brominated phenolic resins and 20 parts of styrene-butadiene rubber(SBR) are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the vulcanizing agent rubber master batch.
3) preparation of promotor rubber master batch: 1 part of promotor 2-benzothiazolyl mercaptan and 10 parts of styrene-butadiene rubber(SBR) are mixed in 120 ℃ of mixing tanks, carry out granulation then, obtain the promotor rubber master batch.
4) dynamic vulcanization: one step of reactivities material, vulcanizing agent rubber master batch, the promotor rubber master batch of above-mentioned three step preparations are joined carry out dynamic vulcanization in 180 ℃ the mixing tank and obtain rubber and plastic than styrene-butadiene rubber(SBR)/acrylonitrile-butadiene-styrene copolymer (SBR/ABS) dynamic vulcanization thermoplastic elastomer that is 60/40.
Comparative Examples 1
Adopt conventional art to prepare rubber and plastic than interior rubber/polypropylene (EPDM/PP) dynamic vulcanization thermoplastic elastomer of the ternary second that is 60/40.Operation steps is as follows:
60 parts of terpolymer EP rubbers (EPDM), 40 parts of polypropylene (PP), 10 parts of fillers, 30 parts of tenderizers, 0.5 part of aging agent, 0.5 part of processing aid are mixed in 180 ℃ of mixing tanks, add 3 parts of vulcanizing agents and 0.6 part of promotor then and carry out dynamic vulcanization and obtain rubber and plastic than EPT rubber (EPDM/PP) dynamic vulcanization thermoplastic elastomer that is 60/40.
Comparative Examples 2
Adopt conventional art to prepare rubber and plastic than nitrile rubber/polypropylene (NBR/PA) dynamic vulcanization thermoplastic elastomer that is 70/30.Operation steps is as follows:
70 parts of paracrils (NBR), 30 parts of polypropylene (PA), 5 parts of fillers, 10 parts of tenderizers, 0.5 part of aging agent, 0.5 part of processing aid are mixed in 200 ℃ of mixing tanks, add 4 parts of vulcanizing agents and 0.7 part of promotor then and carry out dynamic vulcanization and obtain rubber and plastic than EPT rubber (NBR/PA) dynamic vulcanization thermoplastic elastomer that is 70/30.
Choose embodiment 1 and embodiment 2 as determination object from embodiment, the performance data of general's Comparative Examples correspondingly as a reference again.Be shown in Table 1, testing standard all adopts national standard, and test condition is 23 ℃.
Table 1
Wherein, the condition of measuring compression set be the condition of 70 ℃ * 22h, melt flow rate (MFR) be g/10min (230 ℃/5kg).As can be seen from Table 1, the hardness of embodiment 1, tensile set, compression set are less than Comparative Examples 1, and tensile strength, 100% tensile modulus, elongation and melt flow rate (MFR) then are greater than Comparative Examples 1; Same, the hardness of embodiment 2, tensile set, compression set are less than Comparative Examples 1, tensile strength, 100% tensile modulus and melt flow rate (MFR) then are greater than Comparative Examples 1 this illustrate that the prepared elastomerics that goes out of method for preparing thermoplastic elastomer through dynamic vulcanization of the present invention has higher flowability, low compression set, soft, thereby its overall performance is better than the prepared elastomerics that goes out of traditional technology.And elastomerics flowability, low compression set and the soft prepared when being 50/32,62/36,68/35 when rubber and plastic are optimum.