CN109593173A - Have the silicon substrate thermoplastic sulfurized rubber and its synthetic method of anti-flammability - Google Patents
Have the silicon substrate thermoplastic sulfurized rubber and its synthetic method of anti-flammability Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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Abstract
The present invention provides a kind of silicon substrate thermoplastic sulfurized rubber and its synthetic method for having anti-flammability, and it includes provide a flame-proof thermoplastic polyurethane synthesis material, carry out a prepolymer synthesis step and carry out a dynamic vulcanizing step.Flame-proof thermoplastic polyurethane synthesis material includes polyisocyanate compound, macromolecular polyol compound and small molecule polyol.Prepolymer synthesis step is to obtain a silicon substrate thermoplastic sulfurized rubber prepolymer.Dynamic vulcanizing step is to obtain the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability.Whereby, the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability of the present invention has excellent flexility, permanent fire retardant behavior, permanent weatherability, smooth sense and the permanent false characteristics such as wear-resisting.
Description
Technical field
The invention relates to a kind of silicon substrate thermoplastic sulfurized rubbers and its synthetic method for having anti-flammability, especially with regard to one
The silicon substrate thermoplastic sulfurized rubber and its synthetic method of kind halogen-free flame-retardance.
Background technique
In recent years, the application market of silicon substrate thermoplastic sulfurized rubber (TPSiV) is increasingly extensive, and advantage is to have merged thermoplasticity
Two kinds of respective feature performance benefits of material of polyurethane and organosilicon, the sense of touch for having brilliant wearability, silk sliding are lower than thermoplasticity
The skin-friction coefficient of polyurethane still may be used after having excellent gluing, hot air aging with resins such as PC, PC/ABS, ABS
To keep higher physical mechanical property and be readily extruded and the advantages that injection molding, but the shortcomings that silicon substrate thermoplastic sulfurized rubber
It is then without fire-retardant characteristic, so that its application range is limited.
However, known thermoplastic polyurethane rubber (TPU) itself does not have fire-retardant characteristic yet, but there is related dealer to adopt
It is added in thermoplastic polyurethane rubber with halogenated flame retardant, promotes its flame-retarded efficiency.The advantages of halogenated flame retardant is fire-retardant effect
Fruit is good, dosage is few, and price smaller to material properties influence is excellent, but the high molecular material containing halogenated flame retardant in thermal cracking or
A large amount of flue dust and corrosive gas can be generated when burning, is polluted the environment, and related dealer certainly will find other fire retardants
To replace halogenated flame retardant.
In view of this, how to synthesize the silicon substrate thermoplastic sulfurized rubber with anti-flammability, and reduce to caused by environment
Pollution, and can be widely used in miscellaneous industrial products, become the target that related dealer makes great efforts then.
Summary of the invention
One of present invention purpose is to provide a kind of synthetic method of silicon substrate thermoplastic sulfurized rubber for having anti-flammability, is hindered with Halogen
Based on the synthesis material of the thermoplastic polyurethane of combustion property, and silicon-containing compound is added, carries out dynamic vulcanization and reach condensation instead
It answers, the silicon substrate thermoplastic sulfurized rubber of anti-flammability is provided in synthesis.
Another object of the present invention is to provide a kind of silicon substrate thermoplastic sulfurized rubber for having anti-flammability, has permanent weather-proof
Property, smooth sense and the permanent false characteristics such as wear-resisting, and can reduce burning using halogen-free flame retardants when, generates a large amount of poison gas,
Environment protecting is improved, is conducive to expand its application range.
One of present invention embodiment is tied up in a kind of synthetic method for the silicon substrate thermoplastic sulfurized rubber for providing tool anti-flammability,
It includes provide a flame-proof thermoplastic polyurethane synthesis material, carry out a prepolymer synthesis step and carry out a dynamic vulcanization step
Suddenly.Wherein, aforementioned flame-proof thermoplastic polyurethane synthesis material includes polyisocyanate compound, macromolecular polyol compound
And small molecule polyol.Aforementioned prepolymer synthesis step, which is lain in flame-proof thermoplastic polyurethane synthesis material, is added a silicon rubber
Matrix plinth immunomodulator compounds, and be kneaded under a high-speed shearing equipment, to obtain a silicon substrate thermoplastic sulfurized rubber prepolymer.Finally,
Silicon substrate thermoplastic sulfurized rubber prepolymer is put into a double screw extruder by aforementioned dynamic vulcanizing step system, and a silicon rubber is added
Hardener compound after making silicon substrate thermoplastic sulfurized rubber prepolymer and silicon rubber hardener compound melt blending, carries out dynamic
Vulcanize and reach a condensation reaction, to synthesize the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the fire-retardant heat
Plastic polyurethane synthesis material system is to synthesize a flame-proof thermoplastic polyurethane polymer, and the flame-proof thermoplastic polyurethane is poly-
Closing object can be polyester-polyurethane, polyether-polyurethane, polycarbonate polyurethane or its blend.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein with the polyisocyanate
The total weight of cyanate esters is 100 parts by weight, and the content of the macromolecular polyol compound can be 5 parts by weight to 100
Parts by weight, the content of the small molecule polyol can be 5 parts by weight to 100 parts by weight.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the small molecule
Polyalcohol can further include a flame-proof polyol, have the structure one of as shown in formula (1):
Wherein, R is the alkane of hydrogen atom, hydroxy or carbon number 1 to 9
Base, R, it is formula (2) or one of formula (3) is shown structure:
Wherein, RxFor the alkyl or phenyl of carbon number 1 to 4.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein described fire-retardant more
First alcohol can be the dihydric alcohol of DOPO series, and have the structure one of as shown in formula (4), formula (5) or formula (6):
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the silicon rubber
Basic immunomodulator compounds can be the fluid or resin of diorganopolysiloxanecompositions.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the silicon rubber
Basic immunomodulator compounds can be dimethylsiloxane monomer.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the silicon rubber
Hardener compound can contain organic hydride silicon crosslinking agent.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the silicon rubber
Curing agent can be dimethylsiloxane monomer.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein with the polyisocyanate
The total weight of cyanate esters is 100 parts by weight, and the content of silicon rubber basis immunomodulator compounds can be 2 parts by weight to 50 weights
Part is measured, the content of the silicon rubber hardener compound can be 2 parts by weight to 50 parts by weight.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the dynamic sulphur
One filler of addition can be further included by changing step, and the filler can be diorganopolysiloxanecompositions or organic siliconresin.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the filler can
Further include the reinforcing filler of diorganopolysiloxanecompositions.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the dynamic sulphur
One catalyst of addition can be further included by changing step, and the catalyst system reacts to catalyzing and condensing.
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein with the polyisocyanate
The total weight of cyanate esters is 100 parts by weight, and the content of the catalyst can be 0.01 parts by weight to 2 parts by weight.
Another embodiment of the present invention is tied up in providing a kind of silicon substrate thermoplastic sulfurized rubber for having anti-flammability, and the tool hinders
The silicon substrate thermoplastic sulfurized rubber of combustion property is to be synthesized by aforementioned synthetic methods.
The silicon substrate thermoplastic sulfurized rubber of tool anti-flammability according to aforementioned embodiments, wherein the silicon substrate heat of the tool anti-flammability
The limited oxygen index of plasticity vulcanizate can be 27 to 40, and flame retardant property can be V0 grade.
Whereby, the present invention is further synthesized with permanent fire retardant, forever based on flame-proof thermoplastic polyurethane synthesis material
The silicon substrate thermoplastic sulfurized rubber of smooth sense long and the permanent false tool anti-flammability of characteristics such as wear-resisting, and the tool anti-flammability of the present invention
Silicon substrate thermoplastic sulfurized rubber other than having the advantages that general silicon substrate thermoplastic sulfurized rubber, it is stable to also improve uv-resistance, heat
Property, weatherability and increase the characteristic of environment friendly halogen-free fireproof simultaneously, be suitably applied feel and require high, wear-resisting, resistance to UV and fire-retardant etc.
The direct contact type product needed, the handle that can also be applied to portable measuring instrument is encapsulated, industrial waterproof grommet and work
Have the industrial products such as handle.
Detailed description of the invention
For above-mentioned and other purposes, feature, advantage and the embodiment of the present invention can be clearer and more comprehensible, institute's accompanying drawings are said
It is bright as follows:
Fig. 1 shows the synthetic method process of the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability of an embodiment of the present invention
Figure；
Symbol simple declaration: 100: having the synthetic method of the silicon substrate thermoplastic sulfurized rubber of anti-flammability；110,120,130: step
Suddenly.
Specific embodiment
It is following that each embodiment of the present invention will be discussed in greater detail.However, this embodiment can answering for various concept of the invention
With can specifically be carried out in a variety of different particular ranges.Specific embodiment be only for the purpose of description, and it is unrestricted
In the range of exposure.
Referring to FIG. 1, Fig. 1 system is painted the conjunction of the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability of one of present invention embodiment
At the step flow chart of method 100.In Fig. 1, the synthetic method 100 for having the silicon substrate thermoplastic sulfurized rubber of anti-flammability includes step
110, step 120 and step 130.
Step 110 is to provide a flame-proof thermoplastic polyurethane synthesis material, the flame-proof thermoplastic polyurethane synthesis material
Include polyisocyanate compound, macromolecular polyol compound and small molecule polyol.Specifically, the polyisocyanic acid
Ester can be a kind of isocyanates, or can be mixed in any proportion for two kinds or more of isocyanates.Isocyanates is put down
Equal degree of functionality is greater than or equal to 2, for example, isocyanates can be the isocyanates comprising two isocyanate group, include three different
The isocyanates of cyanic acid ester group includes more polyisocyanate-based isocyanates or combinations thereof.
Polyisocyanate compound can be but be not limited to aliphatic diisocyanate, cycloaliphatic ring (cyclo) aliphatic diisocyanates, fragrance
(cyclo) aliphatic diisocyanates or combinations thereof.For example, polyisocyanate compound can be but be not limited to isophorone diisocyanate
(IPDI), hexamethylene diisocyanate (HDI), 2,6- diisocyanate methyl caproate (LDI), toluene di-isocyanate(TDI)
(TDI), 4,4 '-'-diphenylmethane diisocyanates (MDI) and its modifier, polymethylene multi-phenenyl isocyanate (PAPI), naphthalene-
1,5- diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4 '-methylene-dicyclohexyl diisocyanate
(H12MDI) or 1,12- dodecane diisocyanate (C12DD10).One of according to the present invention embodiment, polyisocyanic acid esterification
Closing object can be selected from 4,4 '-'-diphenylmethane diisocyanates (4,4 '-diphenyl methane diisocynate, MDI).
Macromolecular polyol uses molecular weight 200 to 3000 and Weighted Average Functionality more for 2~4 polyether polyol or polyester
First alcohol.Wherein polyether polyol can be but be not limited to polyethylene oxide glycol, polypropylene oxide glycol, polytetrahydrofuran ether glycol
Or homopolymerization or copolymer glycols or the polyalcohol of above-mentioned monomer；Polyester polyol can be a kind of polyester polyol, or can be two kinds
Above polyester polyol is mixed in any proportion, and polyester polyol can be but be not limited to polyethylene glycol adipate two
Alcohol, polyadipate -1,4- butyl glycol ester diol, polyhexamethylene adipate glycol, polycaprolactone glycol or polycarbonate polyol
Alcohol.Embodiment, macromolecular polyol compound can be selected from polypropylene glycol (Polypropylene one of according to the present invention
Glycol, PPG), molecular weight is 700 or 1000 and polytetrahydrofuran ether glycol (Polytetramethylene ether
glycol,PTMEG).And being based on polyisocyanate compound is 100 parts by weight, the content of macromolecular polyol compound can be 5
Parts by weight are to 100 parts by weight.
Small molecule polyol may include expansion agent glycol and flame-proof polyol, wherein expand agent glycol is chain extender again,
It is that strand can be made to extend containing the lower aliphatic or short-chain diol of about 2 to 10 carbon atoms, and the property of polyurethane can be influenced
Energy.Expand agent glycol can be but be not limited to ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4- butanediol, 1,6- oneself two
Alcohol, 1,3-BDO, 1,5-PD, 1,4-CHDM, (ethoxy) ether of quinhydrones two or neopentyl glycol, according to this hair
One of bright embodiment, expanding agent glycol can be selected from 1,4-butanediol (Isosorbide-5-Nitrae-butane diol, BOD).
Flame-proof polyol has anti-flammability, so that flame-proof polyol and the reactant of isocyanates formation also have resistance
Combustion property has the structure one of as shown in formula (1):
Wherein, R is the alkane of hydrogen atom, hydroxy or carbon number 1 to 9
Base, R, it is formula (2) or one of formula (3) is shown structure:
Wherein, RxFor the alkyl or phenyl of carbon number 1 to 4.Embodiment, flame-proof polyol can be DOPO one of according to the present invention
The dihydric alcohol of series, and there is the structure one of as shown in formula (4), formula (5) or formula (6):
Wherein formula (4) is ο-Cresol formaldehyde novolac (CNE, EEW-192), and formula (5) is ο-Cresol
Formaldehyde novolac (CNE, EEW-195), formula (6) be ο-Cresol formaldehyde novolac (CNE,
EEW-200).And being based on polyisocyanate compound is 100 parts by weight, the content of small molecule polyol can be 5 parts by weight to 100
Parts by weight.
Aforementioned DOPO is novel fire retardant, contains P-H key in structure, to alkene, epoxy bond and the great work of carbonyl
Property, it can react and generate many derivatives, DOPO and its derivative are due to containing cyclohexyl biphenyl and phenanthrene ring structure in molecular structure, especially
It is that side phosphorus group is introduced in a manner of cyclic annular O=PO key, and has the characteristic that chemical stability is high and flame retardant property is good.DOPO and
Its derivative can be used as response type and additive flame retardant, has many advantages, such as nontoxic, Halogen, does not migrate and flame retardant property is lasting,
It can be used for a variety of high molecular materials such as polyamide, epoxy resin and polyurethane, make it have fire-retardant characteristic.
Foregoing flame retardant thermoplastic polyurethane synthesis material system is and described to synthesize a flame-proof thermoplastic polyurethane polymer
Flame-proof thermoplastic polyurethane polymer can be polyester-polyurethane, polyether-polyurethane, polycarbonate polyurethane or its blend.
Whereby, polycondensation reaction occurs for above-mentioned polyether polyol or polyester polyol and polyisocyanates reaction monomers, will
The flame-proof polyol of phosphorus-containing groups is introduced directly on the main chain or side chain of unsaturated polyester (UP) strand, relative to the fire-retardant of addition type
Product, will not there is a phenomenon where fire-retardant migrations, product mechanical property, flame retardant property, electric property etc. all can be steady in a long-term.Cause
This, the present invention is based on above-mentioned flame-proof thermoplastic polyurethane synthesis material, and further synthesis has the silicon substrate thermoplastic of anti-flammability
Property vulcanizate.
Step 120 is to carry out a prepolymer synthesis step, is added one in foregoing flame retardant thermoplastic polyurethane synthesis material
Silicon rubber basis immunomodulator compounds, and be kneaded under a high-speed shearing equipment, to obtain a silicon substrate thermoplastic sulfurized rubber prepolymer.Its
Described in silicon rubber basis immunomodulator compounds can for diorganopolysiloxanecompositions (Diorganopolysiloxane) fluid or tree
Rouge, preferably, silicon rubber basis immunomodulator compounds can be dimethylsiloxane monomer-A (Polydimethylsiloxane-
A,PDMS-A).And being based on polyisocyanate compound is 100 parts by weight, the content of silicon rubber basis immunomodulator compounds can be 2 weight
Part to 50 parts by weight.
Step 130 is to carry out a dynamic vulcanizing step, and foregoing silicon substrate thermoplastic sulfurized rubber prepolymer is put into a twin-screw
In extruder, and a silicon rubber hardener compound is added, makes silicon substrate thermoplastic sulfurized rubber prepolymer and silicon rubber curing agent
It after polymer melt is blended, carries out dynamic vulcanization and reaches a condensation reaction, to synthesize the silicon substrate thermoplastic vulcanizates for providing anti-flammability
Glue.Wherein the silicon rubber hardener compound can contain organic hydride silicon crosslinking agent, preferably, the silicon rubber curing agent
Closing object can be dimethylsiloxane monomer-B (Polydimethylsiloxane-B, PDMS-B).And it is esterified based on polyisocyanic acid
Conjunction object is 100 parts by weight, and the content of silicon rubber hardener compound can be 2 parts by weight to 50 parts by weight.
In addition, above-mentioned dynamic vulcanizing step further includes one filler of addition and a catalyst, the filler can be organic for two
Polysiloxanes or organic siliconresin, and the filler further includes the reinforcing filler of diorganopolysiloxanecompositions, wherein two organic poly- silicon
The reinforcing filler of oxygen alkane can be but be not limited to silica or titanium dioxide.One of according to the present invention embodiment, the filler can
Selected from silica, to enhance the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability.And the catalyst system is anti-to catalyzing and condensing
It answers, reaction can just carried out, the total weight based on polyisocyanate compound is 100 parts by weight, and the content of catalyst can be
0.01 parts by weight to 2 parts by weight, and catalyst includes one or two kinds of inorganic tin classes, platinum material catalyst or other carboxylate metals
Salt, amine or similar system of quaternary ammonium compound etc., embodiment, catalyst can be selected from bismuth/platinum catalyst one of according to the present invention.
Whereby, the synthetic method 100 of the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability of the present invention is than traditional multisection type silicon substrate
Thermoplastic sulfurized rubber processing procedure saves at least 30% resource and energy consumption, and allows nanometer grade silicon rubber can be with full and uniform dispersion simultaneously
In flame-proof thermoplastic polyurethane polymer phase, therefore, the silicon substrate thermoplastic sulfurized rubber of synthesized tool anti-flammability is than traditional
Silicon substrate thermoplastic sulfurized rubber has more preferably mechanicalness, weatherability and the false characteristics such as wear-resisting.
The present invention further provides a kind of silicon substrate thermoplastic vulcanizates of tool anti-flammability being synthesized by aforementioned synthetic methods
Glue, measuring limited oxygen index (Limiting Oxygen Index, LOI) according to ASTM D-2863 can be 27 to 40, preferably
Ground, the limited oxygen index of the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability of the present invention can be 35.The limited oxygen index of usual material is 22
The following are combustible materials, are nonflammable material between 22 to 27, are then high nonflammable material 27 or more, and known thermoplastic poly
The limited oxygen index of urethane only 16 to 18, then belongs to combustible material.
The present invention tool anti-flammability silicon substrate thermoplastic sulfurized rubber, flame retardant property can according to UL94 testing vertical flammability,
And measuring condition, at thickness 1.90mm, for flame retardant rating most preferably up to V0 grade, flame retardant rating is the plastics according to different-thickness
The case where burning, classifies, from most being divided into HB, V2, V1 and V0 grade as low as highest.In addition weather resistance is also tested
(48hr, UVA), up to 4 grades or more, reachable -30 DEG C of resistance to low temperature, and can be folding 10 to 200,000 times.
Tradition tool fire resistance thermoplastic polyurethane is added after being and is formed obtained by fire retardant, needs a large amount of fire retardant ability
Reach V0 grade, if silicon substrate thermoplastic sulfurized rubber is made again, mechanical performance can be deteriorated.Therefore the silicon of the tool anti-flammability of the present invention
The advantages of based thermoplastic vulcanizate in addition to after being not required to add fire retardant other than, the silicon substrate thermoplastic sulfurized rubber of synthesized tool anti-flammability
Composition it is more uniform, physical property can be close to the mechanical properties of script thermoplastic polyurethane.
<embodiment>
The silicon substrate thermoplastic sulfurized rubber of the anti-flammability of the present invention is with the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability of the 1st figure
Synthetic method 100 step 110 to step 130 synthesized by and obtain, first using flame-proof thermoplastic polyurethane synthesis material as base
Silicon rubber basis immunomodulator compounds are added in plinth, obtain silicon substrate thermoplastic sulfurized rubber prepolymer under high temperature kneading, then by silicon substrate heat
Plasticity vulcanizate prepolymer is put into double screw extruder, and silicon rubber hardener compound is added, and is carried out dynamic vulcanization and is reached
Condensation reaction, to synthesize the silicon substrate thermoplastic sulfurized rubber for providing anti-flammability.
The flame-proof thermoplastic polyurethane synthesis material system of embodiments of the present invention 1 selects 4,4 '-diphenylmethane diisocyanates
Ester (MDI), polypropylene glycol (PPG), polytetrahydrofuran ether glycol (PTMEG) and 1,4- butanediol (BDO).Initially use one section
Method synthesizes, and first the 1,4-butanediol of the polypropylene glycol of 150g, the polytetrahydrofuran ether glycol of 750g and 36g is added simultaneously
In high shear agitation equipment, to stir 30 minutes at 90 DEG C, the 4 of 400g are added, 4 '-'-diphenylmethane diisocyanates mention
High-temperature to 180 DEG C and stir 5 minutes, be separately added into later 198g ο-Cresol formaldehyde novolac (CNE,
EEW-192) and the dimethylsiloxane monomer-A (PDMS-A) of 250g, persistently stir 3 minutes, to synthesize containing dimethyl
The silicon substrate thermoplastic sulfurized rubber prepolymer of siloxanyl monomers-A.
Then, above-mentioned silicon substrate thermoplastic sulfurized rubber prepolymer is put into double screw extruder, and dimethyl-silicon is added
Oxygen alkane monomer-B (PDMS-B), to be kneaded at a high speed in the environment of 150 DEG C to 200 DEG C, and add bismuth/platinum catalyst of 300ppm into
Mobile state vulcanizes to reach condensation reaction, and the silicon substrate thermoplastic sulfurized rubber of anti-flammability is provided in final synthesis.
The silicon substrate thermoplastic sulfurized rubber and thermoplastic polyurethane and known silicon of the tool anti-flammability of embodiments of the present invention 1
Based thermoplastic vulcanizate, the performance test comparison result under same rigidity, as shown in table 1 below, wherein comparative example 1 is thermoplasticity
Polyurethane, comparative example 2 are known silicon substrate thermoplastic sulfurized rubber.
The flame-proof thermoplastic polyurethane synthesis material system of embodiments of the present invention 2 selects 4,4 '-diphenylmethane diisocyanates
Ester (MDI), polytetrahydrofuran ether glycol (PTMEG) and 1,4- butanediol (BDO).Initially use one-stage process synthesizes, and first will
The polytetrahydrofuran ether glycol of 600g and the 1,4-butanediol of 36g are added in high shear agitation equipment simultaneously, at 90 DEG C
Stirring 30 minutes adds the 4 of 400g, and 4 '-'-diphenylmethane diisocyanates improve temperature to 180 DEG C and stir 5 minutes, it
It is separately added into the ο-Cresol formaldehyde novolac (CNE, EEW-195) of 292g and the dimethyl-silicon of 200g afterwards
Oxygen alkane monomer-A (PDMS-A) is persistently stirred 4 minutes, to synthesize the silicon substrate thermoplasticity sulphur containing dimethylsiloxane monomer-A
Change glue prepolymer.
Then, above-mentioned silicon substrate thermoplastic sulfurized rubber prepolymer is put into double screw extruder, and dimethyl-silicon is added
Oxygen alkane monomer-B (PDMS-B), to be kneaded at a high speed in the environment of 150 DEG C to 200 DEG C, and in addition add the silica of 152g with
And the bismuth of 350ppm/platinum catalyst, dynamic vulcanization is carried out to reach condensation reaction, and the silicon substrate thermoplastic of anti-flammability is provided in final synthesis
Property vulcanizate.
The silicon substrate thermoplastic sulfurized rubber and thermoplastic polyurethane and known silicon of the tool anti-flammability of embodiments of the present invention 2
Based thermoplastic vulcanizate, the performance test comparison result under same rigidity, as shown in table 2 below, wherein comparative example 3 is thermoplasticity
Polyurethane, comparative example 4 are known silicon substrate thermoplastic sulfurized rubber.
By in the result of above-mentioned table 1 and table 2 as it can be seen that under same rigidity, the silicon substrate thermoplasticity of the tool anti-flammability of the present invention
Vulcanizate has excellent anti-flammability, wearability and resistance to compared with known thermoplastic polyurethane and silicon substrate thermoplastic sulfurized rubber
Hou Xing, and silica reinforcing filler added by embodiment 2, so that the engineering properties and hardness of embodiment 2 all enhance.
In conclusion via the present invention tool anti-flammability silicon substrate thermoplastic sulfurized rubber synthetic method synthesized by and it
Have anti-flammability silicon substrate thermoplastic sulfurized rubber have excellent flexility, permanent fire retardant behavior, permanent weatherability, it is smooth sense with
And permanent false characteristics, the added fire retardant such as wear-resisting are halogen-free flame retardants, can postpone fire in the speed of sprawling, also can
Poison gas injury when burning is reduced, and production cost of the present invention is low, the three wastes are few, there is biggish implementary value and social economy to imitate
Benefit.
Although the present invention is disclosed above with embodiment, however, it is not to limit the invention, any to be familiar with this skill
Person may make various changes and modifications without departing from the spirit and scope of the invention, therefore the protection scope of the present invention is worked as
Depending on after subject to attached claim institute defender.
Claims (17)
1. a kind of synthetic method for the silicon substrate thermoplastic sulfurized rubber for having anti-flammability, includes:
A flame-proof thermoplastic polyurethane synthesis material is provided, which is esterified comprising polyisocyanic acid
Close object, macromolecular polyol compound and small molecule polyol；
A prepolymer synthesis step is carried out, a silicon rubber bodying agent chemical combination is added in the flame-proof thermoplastic polyurethane synthesis material
Object, and be kneaded under a high-speed shearing equipment, to obtain a silicon substrate thermoplastic sulfurized rubber prepolymer；And
A dynamic vulcanizing step is carried out, which is put into a double screw extruder, and is added
One silicon rubber hardener compound makes the silicon substrate thermoplastic sulfurized rubber prepolymer and the silicon rubber hardener compound melt blending
Afterwards, it carries out dynamic vulcanization and reaches a condensation reaction, to synthesize the silicon substrate thermoplastic sulfurized rubber of the tool anti-flammability.
2. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that this is fire-retardant
Thermoplastic polyurethane synthesis material system is to synthesize a flame-proof thermoplastic polyurethane polymer, and the flame-proof thermoplastic polyurethane is poly-
Conjunction object is polyester-polyurethane, polyether-polyurethane, polycarbonate polyurethane or its blend.
3. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that more with this
The total weight of isocyanate compound is 100 parts by weight, and the content of the macromolecular polyol compound is 5 parts by weight to 100 weights
Part is measured, the content of the small molecule polyol is 5 parts by weight to 100 parts by weight.
4. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that this small point
Sub- polyalcohol further includes a flame-proof polyol, has the structure one of as shown in formula (1):
Wherein, alkyl of the R for hydrogen atom, hydroxy or carbon number 1 to 9, R, it is formula (2) or one of formula (3) is shown structure:
Wherein, RxFor the alkyl or phenyl of carbon number 1 to 4.
5. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as claimed in claim 4, which is characterized in that this is fire-retardant
Polyalcohol is the dihydric alcohol of DOPO series, and has the structure one of as shown in formula (4), formula (5) or formula (6):
6. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that the silicon rubber
Matrix plinth immunomodulator compounds are the fluid or resin of diorganopolysiloxanecompositions.
7. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as claimed in claim 6, which is characterized in that the silicon rubber
Matrix plinth immunomodulator compounds are dimethylsiloxane monomer.
8. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that the silicon rubber
Glue hardener compound contains organic hydride silicon crosslinking agent.
9. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as claimed in claim 8, which is characterized in that the silicon rubber
Glue hardener compound is dimethylsiloxane monomer.
10. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that with this
The total weight of polyisocyanate compound is 100 parts by weight, and the content of the silicon rubber basis immunomodulator compounds is 2 parts by weight to 50 weights
Part is measured, the content of the silicon rubber hardener compound is 2 parts by weight to 50 parts by weight.
11. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that this is dynamic
State vulcanisation step further includes one filler of addition, and the filler is diorganopolysiloxanecompositions or organic siliconresin.
12. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as claimed in claim 11, which is characterized in that this is filled out
Material further includes the reinforcing filler of diorganopolysiloxanecompositions.
13. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as described in claim 1, which is characterized in that this is dynamic
State vulcanisation step further includes one catalyst of addition, and the catalyst is to be catalyzed the condensation reaction.
14. the synthetic method of the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as claimed in claim 13, which is characterized in that with this
The total weight of polyisocyanate compound is 100 parts by weight, and the content of the catalyst is 0.01 parts by weight to 2 parts by weight.
15. a kind of silicon substrate thermoplastic sulfurized rubber for having anti-flammability, is fire-retardant as the tool as described in claim any one of 1-14
The synthetic method of the silicon substrate thermoplastic sulfurized rubber of property is synthesized into.
16. the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as claimed in claim 15, which is characterized in that the silicon of the tool anti-flammability
The limited oxygen index of based thermoplastic vulcanizate is 27 to 40.
17. the silicon substrate thermoplastic sulfurized rubber of tool anti-flammability as claimed in claim 15, which is characterized in that the silicon of the tool anti-flammability
The flame retardant property of based thermoplastic vulcanizate is V0 grade.
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