CN104845008A - Medical inflaming-retarding elastomer and preparation method thereof - Google Patents
Medical inflaming-retarding elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a medical inflaming-retarding elastomer, which comprises the following raw materials in parts by weight: 100 parts of graft styrene copolymer elastomers, 10 to 50 parts of propylene copolymers, 30 to 150 parts of inorganic flame retardants, 10 to 150 parts of extending oil and 0 to 100 parts of additives, wherein the additives comprise one or several of an antioxidant, a heat stabilizer, an ultraviolet light absorber, an antistatic agent, a dispersing agent, a chlorine scavenging agent, a lubricant, a decomposer, a passivating agent, an inorganic filling agent, a pigment and an antibacterial agent, and the graft structures of the graft styrene copolymer elastomers are imine cyclophosphate formed through a reaction between maleic anhydride and a primary amine-including phosphate compound. The medical inflaming-retarding elastomer obtained by the invention is quite good in inflaming-retarding performance.
Description
Technical field
The present invention relates to medical flame-proof elastomer, also relate to the preparation method of medical flame-proof elastomer, relate to international Patent classificating number C08L53/00.
Background technology
Thermoplastic elastomer TPE(Thermoplastic Elastomer) be a kind of snappiness, high strength, high resilience with rubber, having again can the material of injection molding feature.There is environment-protecting asepsis safety, durometer level is wide, has excellent tint permanence, soft-touch, weathering resistance, fatigue resistance and temperature tolerance, processing characteristics is superior, need not sulfuration, can recycle and reduce costs, both can secondary injection molding, with body material coating and bondings such as PP, PE, PC, PS, ABS, also can be shaping separately.
Existing medical flame-proof elastomer needs to add a large amount of additional fire retardants just can reach LV-0, and this makes the mechanical property of medical flame-proof elastomer greatly reduce, and meanwhile, the elastomerics containing a large amount of additional fire retardant cannot be applied at medical field.
Summary of the invention
In order to solve the problems of the technologies described above, on the one hand, the invention provides a kind of medical flame-proof elastomer, comprise the graft phenylethene analog copolymer elastomerics of 100 weight parts, the acronal of 10-50 weight part, the inorganic combustion inhibitor of 30-150 weight part, the extending oil of 10-150 weight part and the additive of 0-100 weight part, described additive is oxidation inhibitor, thermo-stabilizer, UV light absorber, static inhibitor, dispersion agent, chlorine scavenger, lubricant, decomposition agent, passivator, inorganic filler, pigment, one or more in antiseptic-germicide, the elastomeric Grafting Structure of described graft phenylethene analog copolymer is that maleic anhydride reacts with containing primary amine phosphate compound the imide ring phosphoric acid ester formed, described imide ring phosphate ester structure is:
The main chain bonding of described α, β position and polystyrenic copolymer, described R
1for carbonatoms is the divalent alkyl of 1-8, R
2, R
3be expressed as the univalent alkyl that carbonatoms is 2-5 independently.
As one of embodiments of the present invention, described in aforementioned medical flame-proof elastomer, the percentage of grafting of modified styrenics copolymer elastomer is 0.2-3%.
As one of embodiments of the present invention, R described in aforementioned imide ring phosphate ester structure
1for the divalence branched-chain alkyl that carbonatoms is 3-5.
As one of embodiments of the present invention, R in aforementioned imide ring phosphate ester structure
2, R
3be expressed as the monovalence straight chained alkyl that carbonatoms is 2-5 independently.
As one of embodiments of the present invention, in aforementioned medical flame-proof elastomer, fire retardant is metal hydroxides.
As one of embodiments of the present invention, medical flame-proof elastomer also comprise 1-10 weight part containing amino group Graphene.
As one of embodiments of the present invention, 10-30 weight part described in aforementioned medical flame-proof elastomer containing amino group Graphene be NH
2-PI-g-GO.
As one of embodiments of the present invention, containing in amino group Graphene described in aforementioned medical flame-proof elastomer, nitrogen element and oxygen element are respectively 10at% ~ 15at% and 15at% ~ 20at%.
On the other hand, present invention also offers the preparation method of medical flame-proof elastomer, comprise the following steps:
(1) according to raw material and the weight part of aforementioned medical flame-proof elastomer, prepare raw material, by raw material through double-screw extruding pelletizing, obtain medical flame-proof elastomer particle;
(2) by medical flame-proof elastomer particle, in 170 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 8 hours, then cooling curing obtain.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised more easily can understand present disclosure.Can mention a large amount of term in following specification sheets and claims, these terms are defined as following implication.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context.
" optional " or " optionally " refers to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
Anti-folding line of the present invention refers to that elastomerics is subject to extraneous deformation, makes surface of elastomer occur the folding line that elasticity cannot be recovered.
Medical flame-proof elastomer, comprise the graft phenylethene analog copolymer elastomerics of 100 weight parts, the acronal of 10-50 weight part, the inorganic combustion inhibitor of 30-150 weight part, the extending oil of 10-150 weight part and the additive of 0-100 weight part, described additive is oxidation inhibitor, thermo-stabilizer, UV light absorber, static inhibitor, dispersion agent, chlorine scavenger, lubricant, decomposition agent, passivator, inorganic filler, pigment, one or more in antiseptic-germicide, the elastomeric Grafting Structure of described graft phenylethene analog copolymer is that maleic anhydride reacts with containing primary monoamine compound the imide ring formed.
Described imide ring structure is:
Described α, β are the main chain bonding with polystyrenic copolymer, the divalent alkyl of described R1 to be carbonatoms be 1-8, the univalent alkyl of R2, R3 to be carbonatoms be 2-5.
As one of embodiments of the present invention, styrene copolymer elastomerics comprises the segmented copolymer of styrene-butadiene-styrene, styrene-ethylene-butylene-styrene, styrene butadiene rubbers and styrene-isoprene-phenylethene, but is not limited thereto.
Styrene copolymer elastomerics, such as, can enumerate the polystyrene ABA block polymer (triblock copolymer) such as styrene-butadiene-styrene (SBS), styrene-isoprene-styrene copolymer-(SIS); Polystyrene ABAB types segmented copolymer (Tetrablock copolymer) such as styrene-butadiene-styrene-butadienecopolymer (SBSB), styrene-isoprene-phenylethene-isoprene copolymer (SISI); The polystyrene ABABA type segmented copolymers (five segmented copolymers) such as styrene-butadiene-styrene-butadiene-styrene copolymer (SBSBS), styrene-isoprene-phenylethene-isoprene styrene multipolymer (SISIS); There is the styrene block copolymer etc. of the AB repeating unit more than this.
In addition, as styrene copolymer elastomerics, preferably to use the styrene copolymer elastomerics not by the hydrogenation of ethylenic double bond.As this kind of styrene copolymer elastomerics, such as, can enumerate the multipolymer (SEBSEB) etc. of styrene-ethylene-butadiene multipolymer-styrol copolymer (SEBS), styrene ethylene-propylene multipolymer-styrol copolymer (SEPS), styrene-ethylene-butadiene multipolymer-styrene-ethylene-butadiene multipolymer.
Styrene copolymer elastomerics both can only use a kind, also can use two or more.
In the middle of styrene copolymer elastomerics, preferably there is the styrene copolymer elastomerics of the repeating unit (ABA type, ABAB type, ABABA type etc.) of more than the triblock copolymer be made up of vinylbenzene (A) and divinyl (B).In order to obtain good rebound performance, the ratio of butylene structure shared in the triblock copolymer that vinylbenzene (A) and divinyl (B) are formed is preferably more than 60 % by weight, be more preferably more than 70 % by weight, more preferably more than 75 % by weight.
The elastomeric weight-average molecular weight of styrene copolymer is 5-50 ten thousand.
Acronal, at least a kind of comonomer in the comonomer group of the alpha-olefin can enumerate alfon, selecting free ethylene and carbonatoms to be 4 ~ 10 composition and the multipolymer of propylene.This multipolymer can be random copolymers, also can be segmented copolymer.As this multipolymer, more specifically, can exemplary propylene-ethylene copolymer, propene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-butene-1 copolymer, propylene-ethylene-1-hexene copolymer.As propylene resin, preferred alfon, propylene-ethylene copolymers, propene-1-butene copolymer.They can use one kind or two or more combinationally using.
Described acronal can comprise homopolymer and multipolymer, and 230 DEG C time, under the load of 2.16kg, also has the flow index of 1.0 ~ 90g/10min, preferably, has the flow index of 1.0 ~ 50g/10min.
Described extending oil can select aromatics mineral oil, naphthenic mineral oils, paraffin class mineral oil, preferred paraffin class mineral oil.In addition, preferred molecular-weight average is 300 ~ 1500.
In order to obtain better processing characteristics, acronal of the present invention also can be modified polypropylene resin, described modified polypropylene resin has at least one group in the group of vinylformic acid, toxilic acid, Maleic Acid, Anhydrous, carboxylic acid and oh group composition, more preferably, modified polypropylene resin is that end has acrylic acid modified acroleic acid.
Various additive can be contained within the scope without prejudice to the object of the present invention.As the object lesson of additive, the various oxidation inhibitor such as phenol oxidation inhibitor, Phosphorus oxidation inhibitor, sulfur type antioxidant can be enumerated; The various thermo-stabilizers such as hindered amines thermo-stabilizer; The various UV light absorber such as Benzophenones UV light absorber, Benzotriazole Ultraviolet Stabilizer, benzoate UV light absorber; The various static inhibitor such as non-ionic antistatic agent, cationic antistatic agent, anionic antistatic agent; The various dispersion agents such as bisamide class dispersion agent, paraffin class dispersion agent, organo-metallic salt dispersion agent; The various chlorine scavenger such as the metal carboxylate chlorine scavenger of alkaline earth salt; The various lubricants such as amides lubricant, paraffin class lubricant, organic metal salt series lubricant agent, ester lubricant; The various decomposition agents such as oxide-based decomposition agent, hydrotalcite decomposition agent; The various metal passivators such as hydrazine metalloid passivator, amine metal passivator; The various fire retardants such as brominated organic fire retardant, phosphoric acid based flame retardant, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium hydroxide, red phosphorus; The various inorganic fillers such as talcum powder, mica, clay, calcium carbonate, aluminium hydroxide, magnesium hydroxide, barium sulfate, glass fibre, carbon fiber, silicon-dioxide, Calucium Silicate powder, potassium titanate, wollastonite; Organic filler; Pigment dyestuff; Mineral dye; Inorganic antiseptic; Organic antibacterial agent etc.
Graft phenylethene class elastomerics of the present invention uses maleic anhydride graft styrenic elastomer, re-use and to react containing primary amine phosphate compound and maleic anhydride thus to form imide ring phosphate ester structure, to those skilled in the art, the percentage of grafting of styrenic elastomer is lower, by first obtaining the first time grafting of maleic anhydride, second time graft reaction forms imide ring again, maleic anhydride is very high with amino reactive behavior, imide ring can be obtained efficiently, imide ring and phosphoric acid ester all can obtain good flame retardant resistance to a certain extent, work in coordination with inorganic combustion inhibitor, flame retardant effect and the better medical flame-proof elastomer of mechanical property can be obtained.
Simultaneously, the present inventor is surprised to find that by experiment, the side-chain structure of imide ring phosphoric acid ester and metal hydroxide combustion inhibitor is adopted to have better effect, possible reason is that metal hydroxides is after decompositing a large amount of moisture, impel the decomposition of side chain immediately, the two common flame retardant effect, improve the effect that elastomerics obtains LV-0, and adopt other inorganic combustion inhibitor, then need to use the inorganic combustion inhibitor of more a large amount.So as one of preferred embodiment of the present invention, in aforementioned medical flame-proof elastomer, fire retardant is metal hydroxides.
As one of embodiments of the present invention, R described in aforementioned imide ring phosphate ester structure
1for the divalence branched-chain alkyl that carbonatoms is 3-5.As one of embodiments of the present invention, R in aforementioned imide ring phosphate ester structure
2, R
3be expressed as the monovalence straight chained alkyl that carbonatoms is 2-5 independently.Find in an experiment, in primary amino phosphoric acid ester, R1 uses branched structure, R
2, R
3adopt linear chain structure, better flame retardant effect can be obtained.
As one of embodiments of the present invention, described in aforementioned medical flame-proof elastomer, the percentage of grafting of modified styrenics copolymer elastomer is 0.2-3%.Percentage of grafting be monomer-grafted connect amount/participation grafting in the polymer by the total amount of grafts, too low percentage of grafting makes flame retardant effect of the present invention reduce, and too high percentage of grafting then can cause elastomerics intensity to reduce.The present invention, through a large amount of experiments, show that the percentage of grafting of maleic anhydride be 0.2-3% is most preferably, more has the percentage of grafting of choosing to be 1-2%.
The term " graphene oxide " used in the application is that powdered graphite is through chemical oxidation and the product after peeling off, graphene oxide is single atomic shell, some tens of pm can be expanded at any time on lateral dimension, therefore, its construct trans typical size of general chemistry and Materials science." containing amino group Graphene " in the application refers to the method by modification or grafting, makes in graphite oxide containing active amino.
Containing the amino in amino group Graphene, can react with the anhydride group in MAH-g-SEBS and MAH-g-PP, thus form crosslinking structure, to improve cross-linking density, thus provide Advantageous Effects of the present invention.
In one embodiment, the described amino group Graphene that contains can by electrochemical method preparation (with reference to Chinese patent CN103898612 A), prepared by the method also by chemical graft.
In one preferably embodiment, in described TPE composition is amino-terminated polyimide preformed polymer grafted graphene oxide (NH containing amino group Graphene
2-PI-g-GO), its synthetic method is as follows:
(1) in the there-necked flask of complete drying, add 4, the 4'-benzidines of 1 mole, appropriate meta-cresol and triethylamine, stir under protection of inert gas, after dissolving completely, add the Isosorbide-5-Nitrae of 0.8 ~ 0.9 mole, 5, the phenylformic acid of 8-naphthalenetetracarbacidic acidic dianhydride and 3 moles, after at room temperature stirring 30min, be heated to 75 ~ 85 DEG C, reaction 3.5 ~ 4.5h, again at 175 ~ 185 DEG C, reaction 3.5 ~ 4.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; Filter after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 22 ~ 24h at 50 DEG C, obtain amino-terminated polyimide preformed polymer;
(2) take 50mg graphene oxide and put into 15mLDMF, ultrasonic disperse 0.5 ~ 1h, obtains uniform dispersion.Add the above-mentioned amino-terminated polyimide preformed polymer of 0.2 ~ 0.4g again, ultrasonic disperse 0.5 ~ 1h makes it dissolve completely, above-mentioned dispersion liquid is proceeded to in teflon-lined stainless steel cauldron, 1h is reacted at 120 DEG C, reaction product is after ethanol centrifuge washing three times, and at 30 DEG C, vacuum-drying obtains the graphene oxide of amino-terminated polyimide preformed polymer grafting.
In one preferably mode, in above-mentioned synthetic method, 4,4'-benzidine and Isosorbide-5-Nitrae, the mol ratio of 5,8-naphthalenetetracarbacidic acidic dianhydride is 1:0.85.
In one embodiment, described containing in amino group Graphene, nitrogen element and oxygen element are respectively 10at% ~ 15at% and 15at% ~ 20at%; Preferably, described containing in amino group Graphene, the ratio of nitrogen element and oxygen element is respectively 12at% and 18at%.
In one preferably mode, in above-mentioned synthetic method, 4,4'-benzidine and Isosorbide-5-Nitrae, the mol ratio of 5,8-naphthalenetetracarbacidic acidic dianhydride is 1:0.85.
On the other hand, present invention also offers the preparation method of medical flame-proof elastomer, comprise the following steps:
(1) according to raw material and the weight part of aforementioned medical flame-proof elastomer, prepare raw material, by raw material through double-screw extruding pelletizing, obtain medical flame-proof elastomer particle;
(2) by medical flame-proof elastomer particle, in 170 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 8 hours, then cooling curing obtain.
Graft phenylethene class method for producing elastomers:
Compound is obtained by after styrenic elastomer multipolymer, grafted monomer, initiator mixing;
By the compound melting mixing obtained, there is graft reaction and obtain graft modification styrene analog thermoplastic elastomer.
Embodiment 1, medical flame-proof elastomer, comprise the graft phenylethene analog copolymer elastomerics of 100 weight parts, the acronal of 10-50 weight part, the inorganic combustion inhibitor of 30-150 weight part, the extending oil of 10-150 weight part and the additive of 0-100 weight part, described additive is oxidation inhibitor, thermo-stabilizer, UV light absorber, static inhibitor, dispersion agent, chlorine scavenger, lubricant, decomposition agent, passivator, inorganic filler, pigment, one or more in antiseptic-germicide, the elastomeric Grafting Structure of described graft phenylethene analog copolymer is that maleic anhydride reacts with containing primary amine phosphate compound the imide ring phosphoric acid ester formed, described imide ring phosphate ester structure is:
The main chain bonding of described α, β position and polystyrenic copolymer, described R
1for carbonatoms is the divalent alkyl of 1-8, R
2, R
3be expressed as the univalent alkyl that carbonatoms is 2-5 independently.
Embodiment 2, identical with embodiment 1, difference is, described in aforementioned medical flame-proof elastomer, the percentage of grafting of modified styrenics copolymer elastomer is 0.2-3%.
Embodiment 3, identical with embodiment 1, difference is, R described in aforementioned imide ring phosphate ester structure
1for the divalence branched-chain alkyl that carbonatoms is 3-5.
Embodiment 4, identical with embodiment 1, difference is, R in aforementioned imide ring phosphate ester structure
2, R
3be expressed as the monovalence straight chained alkyl that carbonatoms is 2-5 independently.
Embodiment 5, identical with embodiment 1, difference is, in aforementioned medical flame-proof elastomer, fire retardant is metal hydroxides.
Embodiment 6, identical with embodiment 1, difference is, medical flame-proof elastomer also comprise 1-10 weight part containing amino group Graphene.
Embodiment 7, identical with embodiment 1, difference is, as one of embodiments of the present invention, 10-30 weight part described in aforementioned medical flame-proof elastomer containing amino group Graphene be NH
2-PI-g-GO.
Embodiment 8, identical with embodiment 1, difference is, containing in amino group Graphene described in aforementioned medical flame-proof elastomer, nitrogen element and oxygen element are respectively 10at% ~ 15at% and 15at% ~ 20at%.
Embodiment 9, present invention also offers the preparation method of medical flame-proof elastomer, comprises the following steps:
(1) according to raw material and the weight part of aforementioned medical flame-proof elastomer, prepare raw material, by raw material through double-screw extruding pelletizing, obtain medical flame-proof elastomer particle;
(2) by medical flame-proof elastomer particle, in 170 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 8 hours, then cooling curing obtain.
Hereinafter, by embodiment, the present invention is explained in more detail, but should be understood that these embodiments are only illustrative and nonrestrictive.If do not have other to illustrate, raw materials used is all commercially available.
The present invention is described in detail referring to several example.
Raw material sources:
A1：SEBS
A2:MAH-g-SEBS (percentage of grafting of MAH is 0.5%)
A3:MAH-g-SEBS (percentage of grafting of MAH is 3.1%)
B1：PP
The percentage of grafting of B2:MAH-g-PP(MAH is 2%)
C1:(4-aminobutyl) di(2-ethylhexyl)phosphate propyl ester NH
2cH
2cH
2cH
2cH
2pO (OCH
2cH
2cH
3)
2
C2:(8-aminononyl) diethyl phosphoric acid NH
2cH
2cH
2cH
2cH
2cH
2cH
2cH
2cH
2pO (OCH
2cH
3)
2
C3: amino methyl di(2-ethylhexyl)phosphate pentyl ester NH
2cH
2pO (O CH
2cH
2cH
2cH
2cH
3)
2
Amino-4, the 4-dimethyl propyls of C4:(4-) diethyl phosphoric acid
NH
2CH
2(CH3)
2CH
2CH
2PO(OCH
2CH
3)
2
Amino-4, the 4-dimethyl methyl of C5:(4-) diethyl phosphoric acid
NH
2CH
2(CH3)
2PO(OCH
2CH
3)
2
Amino-4, the 4-dimethyl amyl groups of C6:(4-) diethyl phosphoric acid
NH
2CH
2(CH3)
2CH
2CH
2CH
2CH
2PO(OCH
2CH
3)
2
C7:(8-aminododecane base) diethyl phosphoric acid
D1: containing amino group Graphene (electrochemical production, with reference to Chinese patent CN103898612 A, wherein the ratio of nitrogen element and oxygen element is respectively 10at% and 15at%)
D2: containing amino group Graphene (NH
2-PI-g-GO, wherein 4,4'-benzidines used and Isosorbide-5-Nitrae, the mol ratio of 5,8-naphthalenetetracarbacidic acidic dianhydride is 1:0.8, and the ratio of nitrogen element and oxygen element is respectively 10at% and 15at%)
D3: containing amino group Graphene (NH
2-PI-g-GO, wherein 4,4'-benzidines used and Isosorbide-5-Nitrae, the mol ratio of 5,8-naphthalenetetracarbacidic acidic dianhydride is 1:0.85, and the ratio of nitrogen element and oxygen element is respectively 10at% and 15at%)
D4: containing amino group Graphene (NH
2-PI-g-GO, wherein 4,4'-benzidines used and Isosorbide-5-Nitrae, the mol ratio of 5,8-naphthalenetetracarbacidic acidic dianhydride is 1:0.9, and the ratio of nitrogen element and oxygen element is respectively 10at% and 15at%)
D5: containing amino group Graphene (NH
2-PI-g-GO, wherein 4,4'-benzidines used and Isosorbide-5-Nitrae, the mol ratio of 5,8-naphthalenetetracarbacidic acidic dianhydride is 1:0.85, and the ratio of nitrogen element and oxygen element is respectively 12at% and 18at%)
E1: white oil
F1: potter's clay
G1: zinc oxide
H1 aluminium hydroxide, 2000 orders
H2 magnesium hydroxide, 2000 orders
H3 aluminum oxide, 2000 orders
It should be noted that secondary grafting of the present invention and elastomers technique are placed in same step, certainly, also can separate from technical standpoint, first secondary grafting, then prepare elastomerics.
Embodiment 1
Get A3 100 weight part, the B1 of 28 weight parts, the E1 of 135 weight parts, the F1 of 40 weight parts and the G1 of 0.2 weight part, and the C1 of 10 weight parts, 100 weight parts H1, through double-screw extruding pelletizing, obtain medical flame-proof elastomer particle;
By medical flame-proof elastomer particle, be injected in mould in 170 DEG C ~ 200 DEG C, keep this temperature after 8 hours, then cooling curing obtains the elastomerics of 80mm*10mm*2mm, C1 percentage of grafting is 2.4%.According to UL-94, its flame retardant rating is UL-0., tensile strength 2.3MPa.
Comparative example 1
Identical with embodiment 1, use A1 100 weight part, do not use C1.The elastomerics flame retardant rating obtained is UL-1, tensile strength 2.1MPa.
Comparative example 2
Identical with embodiment 1, use the H3 of 100 weight parts, the elastomerics flame retardant rating obtained is UL-1, tensile strength 2.4MPa.
Embodiment 2
Get A2 100 weight part, the B1 of 28 weight parts, the E1 of 135 weight parts, the F1 of 40 weight parts and the G1 of 0.2 weight part, and the C2 of 10 weight parts, 100 weight parts H1, through double-screw extruding pelletizing, obtain medical flame-proof elastomer particle;
By medical flame-proof elastomer particle, be injected in mould in 170 DEG C ~ 200 DEG C, keep this temperature after 8 hours, then cooling curing obtains the elastomerics of 80mm*10mm*2mm, C1 percentage of grafting is 0.4%.According to UL-94, its flame retardant rating is UL-0, tensile strength 2.8MPa.
Embodiment 3
Identical with embodiment 1, use the C3 of 10 weight parts, according to UL-94, its flame retardant rating is UL-0., tensile strength 3.1MPa.
Embodiment 4
Identical with embodiment 1, use the C4 of 10 weight parts, the H1 of 80 weight parts, according to UL-94, its flame retardant rating is UL-0.
Embodiment 5
Identical with embodiment 1, use the C5 of 10 weight parts, the H1 of 80 weight parts, according to UL-94, its flame retardant rating is UL-0, tensile strength 3.7MPa.
Embodiment 4,5 is all the minimum H1 usage quantitys obtaining UL-0.Visible, use the R1 of branched structure can reduce the usage quantity of H1, and improve tensile strength.
Embodiment 6
Identical with embodiment 1, use the C6 of 10 weight parts, the H1 of 120 weight parts, according to UL-94, its flame retardant rating is UL-0, tensile strength 3.0MPa.
Embodiment 7
Identical with embodiment 1, use the C7 of 10 weight parts, the H1 of 120 weight parts, according to UL-94, its flame retardant rating is UL-0, tensile strength 2.7MPa.
Embodiment employs the too much R1 of carbonatoms, realize UL-O flame retardant rating, need use more filler.
Embodiment 8
Identical with embodiment, the newly-increased D1 employing 20 weight parts, 65 weight part H1, its flame retardant rating is UL-0, tensile strength 4.0MPa.
Embodiment 9
Identical with embodiment, the newly-increased D2 employing 20 weight parts, 65 weight part H1, its flame retardant rating is UL-0, tensile strength 3.9MPa.
Embodiment 10
Identical with embodiment, the newly-increased D3 employing 20 weight parts, 65 weight part H2, its flame retardant rating is UL-0, tensile strength 4.2MPa.
Embodiment 11
Identical with embodiment, the newly-increased D4 employing 20 weight parts, 65 weight part H2, its flame retardant rating is UL-0, tensile strength 4.3MPa.
Embodiment 12
Identical with embodiment, the newly-increased D5 employing 20 weight parts, 65 weight part H1, its flame retardant rating is UL-0, tensile strength 4.4MPa.
Can find out, use technical scheme of the present invention, on acquisition UL-O flame retardant rating, higher tensile strength can be obtained.
Claims (9)
1. medical flame-proof elastomer, comprise the graft phenylethene analog copolymer elastomerics of 100 weight parts, the acronal of 10-50 weight part, the inorganic combustion inhibitor of 30-150 weight part, the extending oil of 10-150 weight part and the additive of 0-100 weight part, described additive is oxidation inhibitor, thermo-stabilizer, UV light absorber, static inhibitor, dispersion agent, chlorine scavenger, lubricant, decomposition agent, passivator, inorganic filler, pigment, one or more in antiseptic-germicide, the elastomeric Grafting Structure of described graft phenylethene analog copolymer is that maleic anhydride reacts with containing primary amine phosphate compound the imide ring phosphoric acid ester formed, described imide ring phosphate ester structure is:
The main chain bonding of described α, β position and polystyrenic copolymer, described R
1for carbonatoms is the divalent alkyl of 1-8, R
2, R
3be expressed as the univalent alkyl that carbonatoms is 2-5 independently.
2. medical flame-proof elastomer according to claim 1, is characterized in that, the percentage of grafting of described modified styrenics copolymer elastomer is 0.2-3%.
3. medical flame-proof elastomer according to claim 1, is characterized in that, R described in described imide ring phosphate ester structure
1for the divalence branched-chain alkyl that carbonatoms is 3-5.
4. medical flame-proof elastomer according to claim 1, is characterized in that, R in described imide ring phosphate ester structure
2, R
3be expressed as the monovalence straight chained alkyl that carbonatoms is 2-5 independently.
5. medical flame-proof elastomer according to claim 1, is characterized in that, in medical flame-proof elastomer, fire retardant is metal hydroxides.
6. medical flame-proof elastomer according to claim 1, is characterized in that, described medical flame-proof elastomer also comprise 1-10 weight part containing amino group Graphene.
7. medical flame-proof elastomer according to claim 1, is characterized in that, 10-30 weight part described in described medical flame-proof elastomer containing amino group Graphene be NH
2-PI-g-GO.
8. medical flame-proof elastomer according to claim 1, is characterized in that, described containing in amino group Graphene, nitrogen element and oxygen element are respectively 10at% ~ 15at% and 15at% ~ 20at%.
9. the preparation method of medical flame-proof elastomer, comprises the following steps:
(1) according to raw material and the weight part of the medical flame-proof elastomer in claim 1-8 described in any one claim, prepare raw material, by raw material through double-screw extruding pelletizing, obtain medical flame-proof elastomer particle;
(2) by medical flame-proof elastomer particle, in 170 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 8 hours, then cooling curing obtain.
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