CN105860355B - High ferro high fire-retardance high durable rubber floor covering and preparation method thereof - Google Patents
High ferro high fire-retardance high durable rubber floor covering and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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Abstract
The invention discloses a kind of high ferro high fire-retardance high durable rubber floor coverings, by including that PVC, EVA g MAH, natural rubber, butadiene-styrene rubber, double amino-polyethyleneglycols modification hyperbranched poly pyrrole throat, filler, barium/zinc composite stabilizer, KH 560, paraffin and stearic raw material are prepared.The invention also discloses the high ferro preparation methods of high fire-retardance high durable rubber floor covering.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly it relates to which a kind of high ferro is resistance to high fire-retardance height
Wait rubber floor covering and preparation method thereof.
Background technology
In recent years, increasing to the demand on high ferro floor with the rapid development of high-speed railway.But due to
Using in high ferro, there is very high requirement to the intensity on floor, elasticity, weatherability and anti-flammability.In the prior art, generally
Using polyvinylchloride and rubber as the bulk composition on floor, have in intensity, elasticity, weatherability and anti-flammability
It is insufficient, it is difficult to fully meet the demand of high ferro.In addition, in order to improve anti-flammability, inorganic combustion inhibitor is generally added in the prior art
Improve its performance, but there is compatible, easy reunion with high molecular material in inorganic material, but also material can be caused
The decline of mechanical property, it is difficult to obtain the high ferro flooring material of excellent combination property.
Hence it is highly desirable to by formula and production technology improvement, with obtain one kind have high intensity, high resiliency,
The high ferro floor of high-weatherability and the excellent combination property of high flame retardant.
Invention content
To solve the above-mentioned problems, one aspect of the present invention provides a kind of high ferro high fire-retardance high durable rubber floor covering,
It is prepared by the raw material including following parts by weight：
Preferably, high ferro high fire-retardance high durable rubber floor covering, is prepared by the raw material including following parts by weight：
In one embodiment, the average degree of polymerization of the PVC is 800~1500；Preferably, the PVC is averaged
The degree of polymerization is 930.
In one embodiment, in the EVA-g-MAH, the grafting rate of MAH is 1%~6%；Preferably, described
In EVA-g-MAH, the grafting rate of MAH is 3%.
In one embodiment, the double amino-polyethyleneglycols modification hyperbranched poly pyrrole throat prepared by following methods and
At：
(1) the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride is prepared
1 mole of three acid anhydrides and appropriate metacresol are added in the three-necked flask being completely dried, stirs under inert gas protection
It mixes, after three acid anhydrides are completely dissolved, 0.5~1.2 mole of tetramine is added, after 30min is stirred at room temperature, is heated to 75~85
DEG C, 3.5~4.5h is reacted, then at 175~185 DEG C, reacts 3.5~4.5h；After reaction, room temperature is down to get naphthalene anhydride
Terminated hyperbranched poly- pyrrole throat solution；
(2) double amino-polyethyleneglycols are prepared and modify hyperbranched poly pyrrole throat
In the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride obtained toward step (2), 0.3~2 mole of the poly- second of double amino is added
Glycol after 30min is stirred at room temperature under inert gas protection, is heated to 75~85 DEG C, reacts 3.5~4.5h, then 175~
At 185 DEG C, 3.5~4.5h is reacted；After reaction, it is down to room temperature, solution is poured into methanol, there is Precipitation；Use methanol
Repeatedly washing removal solvent after filter after, in vacuum drying oven at 50 DEG C drying 22~for 24 hours to get double amino-polyethyleneglycols modify
Hyperbranched poly pyrrole throat.
In one embodiment, three acid anhydride is 1,3,5- tri- (4- naphthoxys -1,8- diacid) benzene, three acid anhydride.
In one embodiment, the tetramine for being used to prepare double amino-polyethyleneglycols modification hyperbranched poly pyrrole throats
Selected from 3,3 '-diaminobenzidines, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, 3,3 ', 4,
Any one or more in 4 '-tetramino benzophenone, 1,2,4,5- tetramino benzene, 1,2,5,6- tetramino naphthalenes；Preferably,
The tetramine is 3,3 ', 4,4 '-tetramino diphenyl ether.
In one embodiment, the average degree of polymerization of double amino-polyethyleneglycols be selected from 44,89,112,135,180,
226, any one in 453,1135 and 2271；Preferably, the average degree of polymerization of double amino-polyethyleneglycols is 226.
In one embodiment, the filler is polybenzimidazoles coated silica compound particle, and the polyphenyl
And imidazoles coated silica compound particle is prepared by following methods：
(1) preparation of amino-terminated polybenzimidazoles prepolymer
0.1 mole of tetramine is first dissolved in 1000 grams of polyphosphoric acids containing 85wt% phosphorus pentoxides, then will
0.05~0.09 mole of diacid is added in reaction solution, after being reacted 15 hours at 220 DEG C, is down to room temperature, in precipitating to water, so
It is neutralized afterwards with ammonium hydroxide, filters, be dried in vacuo at 100 DEG C, obtain amino-terminated polybenzimidazoles prepolymer；
(2) preparation of silane-modified silica
Be added in the metal reaction container with blender, thermometer and condenser pipe of 1000mL deionized water 100mL,
After KH-560 1g, it is slowly added into hydrophilic silicon oxides 20g under stiring, by filtering after reacting 30 minutes at room temperature
To silane-modified silica；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL are added in the beaker of 300mL,
After 70 DEG C of stirring and dissolvings, above-mentioned silane-modified silica 1 5g is added and is warming up to 80 DEG C it is stirred 2 hours；Then will
Mixture pours into deionized water, and filters, and filter cake is dried in vacuo at 120 DEG C and obtains within 4 hours polybenzimidazoles cladding dioxy
SiClx compound particle.
In one embodiment, the diacid be selected from adipic acid, glutaric acid, pimelic acid, decanedioic acid, dodecanedioic acid,
In terephthalic acid (TPA), M-phthalic acid, 2,2 '-biphenyl dicarboxylic acids, 4,4 '-biphenyl dicarboxylic acids and 5- amino isophthalic acids
Any one or more；Preferably, the diacid is 5- amino isophthalic acids.
In one embodiment, the tetramine for being used to prepare polybenzimidazoles coated silica compound particle is selected from
3,3 '-diaminobenzidines, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, 3,3 ', 4,4 '-four
Aminobenzophenone, 1, any one or more in 2,4,5- tetramino benzene, 1,2,5,6- tetramino naphthalenes；Preferably, described
Tetramine is 3,3 '-diaminobenzidines.
Another aspect of the present invention provides the preparation method of the high ferro high fire-retardance high durable rubber floor covering, including following
Step：
(1) the mixed machine of heat is added in the raw material, is premixed, is dried under 110 DEG C of -130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 40 DEG C -50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195-205 DEG C, 185-195 DEG C,
175-185℃、170-180℃；
The molding die temperature of the extruder is followed successively by 155-165 DEG C, 160-170 along the direction of propulsion of the material
℃、165-175℃、175-185℃、195-205℃。
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Specific implementation mode
With reference to preferred embodiment of the invention below detailed description and including embodiment can be more easily understood
Present disclosure.A large amount of term is referred in following description and claims, these terms are defined
For with following meanings.
" optional " or " optionally " refer to that subsequently described event or item may or may not occur, and the description
The situation that the situation and event occurred including event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the equipment of detection numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
Equivalent, concentration or other values or parameter are preferred with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that value limit is walked, this, which should be understood as, specifically discloses by under any range limit or preferred value and any range
Any pairing of limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when disclosing
When range " l to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-
3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range intention include its end value and
All integers within the scope of this and score.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
One aspect of the present invention provides a kind of high ferro high fire-retardance high durable rubber floor covering, by including following parts by weight
Raw material is prepared：
Preferably, high ferro high fire-retardance high durable rubber floor covering, is prepared by the raw material including following parts by weight：
PVC
PVC for the application is not particularly limited, and can be commercially available arbitrary commercially produced product.
In one embodiment, the average degree of polymerization of the PVC is 800~1500；It is highly preferred that the PVC's is flat
Right homopolymerization is 930.
EVA-g-MAH
Maleic anhydride modified vinyl acetate co-polymer (EVA-g-MAH) in the application is not particularly limited, Ke Yiwei
It is commercially available or experiment synthesis, such as two methods of solution graft copolymerization and the synthesis of fusion-grafting may be used.
In one embodiment, in the EVA-g-MAH, the grafting rate of MAH is 1%~6%；Preferably, described
In EVA-g-MAH, the grafting rate of MAH is 3%.
Natural rubber
Natural rubber in the application is not particularly limited, and can be commercially available arbitrary commercially produced product.
Butadiene-styrene rubber
Butadiene-styrene rubber in the application is not particularly limited, and can be commercially available arbitrary commercially produced product.
Double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat
Double amino-polyethyleneglycols modification hyperbranched poly pyrrole throat in the application is blocked by double amino-polyethyleneglycols and naphthalene anhydride
Hyperbranched poly pyrrole throat be obtained by the reaction.
In one embodiment, the double amino-polyethyleneglycols modification hyperbranched poly pyrrole throat prepared by following methods and
At：
(1) the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride is prepared
1 mole of three acid anhydrides and appropriate metacresol are added in the three-necked flask being completely dried, stirs under inert gas protection
It mixes, after three acid anhydrides are completely dissolved, 0.5~1.2 mole of tetramine is added, after 30min is stirred at room temperature, is heated to 75~85
DEG C, 3.5~4.5h is reacted, then at 175~185 DEG C, reacts 3.5~4.5h；After reaction, room temperature is down to get naphthalene anhydride
Terminated hyperbranched poly- pyrrole throat solution；
(2) double amino-polyethyleneglycols are prepared and modify hyperbranched poly pyrrole throat
In the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride obtained toward step (2), 0.3~2 mole of the poly- second of double amino is added
Glycol after 30min is stirred at room temperature under inert gas protection, is heated to 75~85 DEG C, reacts 3.5~4.5h, then 175~
At 185 DEG C, 3.5~4.5h is reacted；After reaction, it is down to room temperature, solution is poured into methanol, there is Precipitation；Use methanol
Repeatedly washing removal solvent after filter after, in vacuum drying oven at 50 DEG C drying 22~for 24 hours to get double amino-polyethyleneglycols modify
Hyperbranched poly pyrrole throat.
It is preferably carried out in mode in one kind, the preparation method of double amino-polyethyleneglycols modification hyperbranched poly pyrrole throats
In, the molar ratio of three acid anhydrides, tetramine and double amino-polyethyleneglycols is 1:1:1.
In one embodiment, three acid anhydride is 1,3,5- tri- (4- naphthoxys -1,8- diacid) benzene, three acid anhydride.
In one embodiment, three acid anhydride of described 1,3,5- tri- (4- naphthoxys -1,8- diacid) benzene is prepared by following methods
It obtains：
In the 100mL three-necked bottles equipped with nitrogen inlet, magnetic agitation, water knockout drum and reflux condensing tube, it is added 0.6305
Gram (5mmol) phloroglucinol, 8mL methanol, 0.60 gram of (15mmol) sodium hydroxide are warming up to 100 DEG C, steam methanol and
Water is evaporated postcooling, is cooled to room temperature, and 4.156 grams of bromo- 1,8- naphthalene anhydrides of (15mmol) 4-, 10mL N- methyl are added into reaction bulb
Acetamide is warming up to 120 DEG C, and 15mL toluene to dropping funel is instilled reaction system, is warming up to 140 DEG C, is reacted 4 hours, is steamed
Go out toluene, be warming up to 150 DEG C, the reaction was continued 22 hours, and after reaction, system is cooled to room temperature.Then product is poured into
In 100mL acetone, the solid that is precipitated in system filters after being washed with water, and is dried in vacuo, obtains 2.58 grams of crude product.It is obtained
Crude product is recrystallized with acetic anhydride, obtains 1.53 grams of pure products, yield 42.9%.
In one embodiment, the tetramine for being used to prepare double amino-polyethyleneglycols modification hyperbranched poly pyrrole throats
Selected from 3,3 '-diaminobenzidines, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, 3,3 ', 4,
Any one or more in 4 '-tetramino benzophenone, 1,2,4,5- tetramino benzene, 1,2,5,6- tetramino naphthalenes；Preferably,
The tetramine is 3,3 ', 4,4 '-tetramino diphenyl ether.
In one embodiment, the average degree of polymerization of double amino-polyethyleneglycols be selected from 44,89,112,135,180,
226, any one in 453,1135 and 2271；Preferably, the average degree of polymerization of double amino-polyethyleneglycols is 226.
Poly- pyrrole throat has excellent weatherability, higher intensity and good flame retardant property, but general poly- pyrrole throat
Without good processing performance, and hardly possible is compatible well with PVC, is overspend by the modification and selection of double amino-polyethyleneglycols
Change structure, compatibility and processing problems can be efficiently solved, in addition, the presence of a large amount of amino, it can be as the friendship of system
Join point, greatly improve mechanical strength, to provide the advantageous effects of the present invention.
Filler
Filler in the application is not particularly limited, and can be that commercially available arbitrary commercially produced product or synthesis obtain.Such as carbon
Sour calcium, hydrophilic silicon oxides or polybenzimidazoles coated silica compound particle, but preferably, the filler be polyphenyl simultaneously
Imidazoles coated silica compound particle, and the polybenzimidazoles coated silica compound particle by following methods prepare and
At：
(1) preparation of amino-terminated polybenzimidazoles prepolymer
0.1 mole of tetramine is first dissolved in 1000 grams of polyphosphoric acids containing 85wt% phosphorus pentoxides, then will
0.05~0.09 mole of diacid is added in reaction solution, after being reacted 15 hours at 220 DEG C, is down to room temperature, in precipitating to water, so
It is neutralized afterwards with ammonium hydroxide, filters, be dried in vacuo at 100 DEG C, obtain amino-terminated polybenzimidazoles prepolymer；
(2) preparation of silane-modified silica
Be added in the metal reaction container with blender, thermometer and condenser pipe of 1000mL deionized water 100mL,
After KH-560 1g, it is slowly added into hydrophilic silicon oxides 20g under stiring, by filtering after reacting 30 minutes at room temperature
To silane-modified silica；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL are added in the beaker of 300mL,
After 70 DEG C of stirring and dissolvings, above-mentioned silane-modified silica 1 5g is added and is warming up to 80 DEG C it is stirred 2 hours；Then will
Mixture pours into deionized water, and filters, and filter cake is dried in vacuo at 120 DEG C and obtains within 4 hours polybenzimidazoles cladding dioxy
SiClx compound particle.
It is preferably carried out in mode in one kind, the molar ratio of tetramine and diacid is 1:0.9.
In one embodiment, the diacid be selected from adipic acid, glutaric acid, pimelic acid, decanedioic acid, dodecanedioic acid,
In terephthalic acid (TPA), M-phthalic acid, 2,2 '-biphenyl dicarboxylic acids, 4,4 '-biphenyl dicarboxylic acids and 5- amino isophthalic acids
Any one or more；Preferably, the diacid is 5- amino isophthalic acids.
In one embodiment, the tetramine for being used to prepare polybenzimidazoles coated silica compound particle is selected from
3,3 '-diaminobenzidines, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s, 3,3 ', 4,4 '-four
Aminobenzophenone, 1, any one or more in 2,4,5- tetramino benzene, 1,2,5,6- tetramino naphthalenes；Preferably, described
Tetramine is 3,3 '-diaminobenzidines.
Polybenzimidazoles can effectively quench free radical, and to improve the ageing-resistant performance of system, polybenzimidazoles is also in addition
Extraordinary fire proofing, is added by the mode compound with silica, has both solved polybenzimidazoles and the compatible of PVC is asked
Topic also can guarantee that silica will not reunite, and be dispersed in system well, to provide the Advantageous effect of the present invention
Fruit.
Barium/zinc composite stabilizer
Barium/zinc composite stabilizer in the application is not particularly limited, and can be commercially available arbitrary commercially produced product.
KH-560
Epoxy silane coupling agent KH-560 in the application is not particularly limited, and can be commercially available arbitrary commercialization production
Product.
Paraffin
Paraffin in the application is not particularly limited, and can be commercially available arbitrary commercially produced product.
Stearic acid
Stearic acid in the application is not particularly limited, and can be commercially available arbitrary commercially produced product.
Another aspect of the present invention provides the preparation method of the high ferro high fire-retardance high durable rubber floor covering, including following
Step：
(1) the mixed machine of heat is added in the raw material, is premixed, is dried under 110 DEG C of -130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 40 DEG C -50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195-205 DEG C, 185-195 DEG C,
175-185℃、170-180℃；
The molding die temperature of the extruder is followed successively by 155-165 DEG C, 160-170 along the direction of propulsion of the material
℃、165-175℃、175-185℃、195-205℃。
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, and number used in following material is weight
Part.
Raw material：
All tetramines, diacid are purchased from CTI, SigmaAldrich, AlfaAesar or SCRC, and directly use, and are not necessarily to
It is further purified.Hydrophilic silicon oxides (dry vapor silica) are purchased from Shenyang Chemical Co., Ltd..KH-560、
Calcium carbonate is purchased from Sinopharm Chemical Reagent Co., Ltd..Other raw materials are purchased from Aladdin reagent Co., Ltd.
A1：PVC (average degree of polymerization 800)
A2：PVC (average degree of polymerization 1500)
A3：PVC (average degree of polymerization 930)
B1：EVA-g-MAH (MAH grafting rates are 1%)
B2：EVA-g-MAH (MAH grafting rates are 6%)
B3：EVA-g-MAH (MAH grafting rates are 3%)
C1：Natural rubber
D1：Butadiene-styrene rubber
E1：Double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat, are prepared by following methods：
(1) the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride is prepared
In the three-necked flask being completely dried be added 1 mole 1,3,5- tri- (4- naphthoxys -1,8- diacid) benzene, three acid anhydride and
2000ml metacresols, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.5 mole of 3,3 '-benzidines are added
Amine after 30min is stirred at room temperature, is heated to 85 DEG C, reacts 3.5h, then at 185 DEG C, reacts 4.5h；After reaction, it drops
To room temperature to get the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride；
(2) double amino-polyethyleneglycols are prepared and modify hyperbranched poly pyrrole throat
In the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride obtained toward step (2), 2 moles of double amino-polyethyleneglycols are added,
After 30min is stirred at room temperature under nitrogen protection, 85 DEG C are heated to, reacts 4.5h, then at 185 DEG C, reacts 4.5h；Reaction terminates
Afterwards, it is down to room temperature, solution is poured into methanol, there is Precipitation；It is washed repeatedly with methanol after being filtered after removing solvent, in vacuum
It is dried at 50 DEG C in baking oven and modifies hyperbranched poly pyrrole throat for 24 hours to get double amino-polyethyleneglycols.
E2：Double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat, are prepared by following methods：
(1) the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride is prepared
In the three-necked flask being completely dried be added 1 mole 1,3,5- tri- (4- naphthoxys -1,8- diacid) benzene, three acid anhydride and
2000ml metacresols, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 1 mole of 3,3 '-diaminobenzidines are added,
After 30min is stirred at room temperature, 85 DEG C are heated to, reacts 3.5h, then at 185 DEG C, reacts 4.5h；After reaction, it is down to
Room temperature is to get the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride；
(2) double amino-polyethyleneglycols are prepared and modify hyperbranched poly pyrrole throat
In the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride obtained toward step (2), 1 mole of double amino-polyethyleneglycols are added,
After 30min is stirred at room temperature under nitrogen protection, 85 DEG C are heated to, reacts 4.5h, then at 185 DEG C, reacts 4.5h；Reaction terminates
Afterwards, it is down to room temperature, solution is poured into methanol, there is Precipitation；It is washed repeatedly with methanol after being filtered after removing solvent, in vacuum
It is dried at 50 DEG C in baking oven and modifies hyperbranched poly pyrrole throat for 24 hours to get double amino-polyethyleneglycols.
E3：
Double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat, are prepared by following methods：
(1) the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride is prepared
In the three-necked flask being completely dried be added 1 mole 1,3,5- tri- (4- naphthoxys -1,8- diacid) benzene, three acid anhydride and
2000ml metacresols, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 1 mole of 3,3 ', 4,4 '-tetraminos two are added
Phenylate after 30min is stirred at room temperature, is heated to 85 DEG C, reacts 3.5h, then at 185 DEG C, reacts 4.5h；After reaction,
Room temperature is down to get the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride；
(2) double amino-polyethyleneglycols are prepared and modify hyperbranched poly pyrrole throat
In the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride obtained toward step (2), 1 mole of double amino-polyethyleneglycols are added,
After 30min is stirred at room temperature under nitrogen protection, 85 DEG C are heated to, reacts 4.5h, then at 185 DEG C, reacts 4.5h；Reaction terminates
Afterwards, it is down to room temperature, solution is poured into methanol, there is Precipitation；It is washed repeatedly with methanol after being filtered after removing solvent, in vacuum
It is dried at 50 DEG C in baking oven and modifies hyperbranched poly pyrrole throat for 24 hours to get double amino-polyethyleneglycols.
F1：Calcium carbonate
F2：Hydrophilic silicon oxides (dry vapor silica)
F3：Polybenzimidazoles coated silica compound particle is prepared by following methods：
(1) preparation of amino-terminated polybenzimidazoles prepolymer
By 0.1 mole 3,3 ', 4,4 '-tetramino diphenyl ether be first dissolved in containing 85wt% phosphorus pentoxides more than 1000 grams
In polyphosphoric acid, then 0.05 mole of terephthalic acid (TPA) is added in reaction solution, after being reacted 15 hours at 220 DEG C, is down to room
Temperature in precipitating to water, is then neutralized with ammonium hydroxide, is filtered, is dried in vacuo at 100 DEG C, it is pre- to obtain amino-terminated polybenzimidazoles
Polymers；
(2) preparation of silane-modified silica
Be added in the metal reaction container with blender, thermometer and condenser pipe of 1000mL deionized water 100mL,
After KH-560 1g, it is slowly added into hydrophilic silicon oxides 20g under stiring, by filtering after reacting 30 minutes at room temperature
To silane-modified silica；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL are added in the beaker of 300mL,
After 70 DEG C of stirring and dissolvings, above-mentioned silane-modified silica 1 5g is added and is warming up to 80 DEG C it is stirred 2 hours；Then will
Mixture pours into deionized water, and filters, and filter cake is dried in vacuo at 120 DEG C and obtains within 4 hours polybenzimidazoles cladding dioxy
SiClx compound particle.
F4：Polybenzimidazoles coated silica compound particle is prepared by following methods：
(1) preparation of amino-terminated polybenzimidazoles prepolymer
By 0.1 mole 3,3 '-diaminobenzidines are first dissolved in 1000 grams of poly phosphorus containing 85wt% phosphorus pentoxides
In acid, then 0.09 mole of 5- amino isophthalic acids are added in reaction solution, after being reacted 15 hours at 220 DEG C, are down to
Room temperature in precipitating to water, is then neutralized with ammonium hydroxide, is filtered, is dried in vacuo at 100 DEG C, obtains amino-terminated polybenzimidazoles
Prepolymer；
(2) preparation of silane-modified silica
Be added in the metal reaction container with blender, thermometer and condenser pipe of 1000mL deionized water 100mL,
After KH-560 1g, it is slowly added into hydrophilic silicon oxides 20g under stiring, by filtering after reacting 30 minutes at room temperature
To silane-modified silica；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL are added in the beaker of 300mL,
After 70 DEG C of stirring and dissolvings, above-mentioned silane-modified silica 1 5g is added and is warming up to 80 DEG C it is stirred 2 hours；Then will
Mixture pours into deionized water, and filters, and filter cake is dried in vacuo at 120 DEG C and obtains within 4 hours polybenzimidazoles cladding dioxy
SiClx compound particle.
G1：Barium/zinc composite stabilizer
H1：KH-560
I1：Paraffin
J1：Stearic acid
Embodiment 1
By the A1 of 100 parts by weight, the B1 of 20 parts by weight, the C1 of 10 parts by weight, the D1 of 5 parts by weight, the E1 of 5 parts by weight, 10
The mixed machine of J1 addition heat of the F1 of parts by weight, the G1 of 1 parts by weight, the H1 of 2 parts by weight, the I1 of 1 parts by weight and 0.5 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Embodiment 2
By the A2 of 100 parts by weight, the B2 of 50 parts by weight, the C1 of 25 parts by weight, the D1 of 8 parts by weight, the E1 of 20 parts by weight, 50
The mixed machine of J1 addition heat of the F1 of parts by weight, the G1 of 40 parts by weight, the H1 of 8 parts by weight, the I1 of 5 parts by weight and 2 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Embodiment 3
By the A3 of 100 parts by weight, the B3 of 25 parts by weight, the C1 of 30 parts by weight, the D1 of 10 parts by weight, 15 parts by weight E1,
The mixed machine of J1 addition heat of the F1 of 40 parts by weight, the G1 of 20 parts by weight, the H1 of 7 parts by weight, the I1 of 4 parts by weight and 1 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Embodiment 4
By the A3 of 100 parts by weight, the B3 of 25 parts by weight, the C1 of 30 parts by weight, the D1 of 10 parts by weight, 15 parts by weight E2,
The mixed machine of J1 addition heat of the F1 of 40 parts by weight, the G1 of 20 parts by weight, the H1 of 7 parts by weight, the I1 of 4 parts by weight and 1 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Embodiment 5
By the A3 of 100 parts by weight, the B3 of 25 parts by weight, the C1 of 30 parts by weight, the D1 of 10 parts by weight, 15 parts by weight E3,
The mixed machine of J1 addition heat of the F1 of 40 parts by weight, the G1 of 20 parts by weight, the H1 of 7 parts by weight, the I1 of 4 parts by weight and 1 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Embodiment 6
By the A3 of 100 parts by weight, the B3 of 25 parts by weight, the C1 of 30 parts by weight, the D1 of 10 parts by weight, 15 parts by weight E3,
The mixed machine of J1 addition heat of the F2 of 40 parts by weight, the G1 of 20 parts by weight, the H1 of 7 parts by weight, the I1 of 4 parts by weight and 1 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Embodiment 7
By the A3 of 100 parts by weight, the B3 of 25 parts by weight, the C1 of 30 parts by weight, the D1 of 10 parts by weight, 15 parts by weight E3,
The mixed machine of J1 addition heat of the F3 of 40 parts by weight, the G1 of 20 parts by weight, the H1 of 7 parts by weight, the I1 of 4 parts by weight and 1 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Embodiment 8
By the A3 of 100 parts by weight, the B3 of 25 parts by weight, the C1 of 30 parts by weight, the D1 of 10 parts by weight, 15 parts by weight E3,
The mixed machine of J1 addition heat of the F4 of 40 parts by weight, the G1 of 20 parts by weight, the H1 of 7 parts by weight, the I1 of 4 parts by weight and 1 parts by weight,
It premixed, dried under 130 DEG C of temperature conditions；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Comparative example 1
By the A3 of 100 parts by weight, the B3 of 25 parts by weight, the C1 of 30 parts by weight, the D1 of 10 parts by weight, 40 parts by weight F4,
The mixed machine of J1 addition heat of the G1 of 20 parts by weight, the H1 of 7 parts by weight, the I1 of 4 parts by weight and 1 parts by weight, in 130 DEG C of temperature conditions
Under premixed, dried；
(2) it is sent into extruder after the material after drying being cooled to 50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder, along the direction of propulsion of the material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C, 180
℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155 DEG C, 160 DEG C, 165 DEG C,
185℃、195℃。
Test method
Tensile strength and elongation at break：According to GB/T 1040-92 standard testings.
Weatherability is tested：Gained floor is immersed in the sodium hydrate aqueous solution of 50 DEG C of 1mol/L, is surveyed after 24 hours
Try its loss of tensile strength rate；Gained floor is immersed in the aqueous sulfuric acid of 50 DEG C of 1mol/L, it is tested after 24 hours
Loss of tensile strength rate.
Flame retardant property：According to 2046 standard test oxygen index (OI)s of GB/T
Test result is shown in Table 1.
Table 1
Data above can be seen that modifies hyperbranched poly pyrrole throat and polybenzimidazoles with without using double amino-polyethyleneglycols
The product of coated silica compound particle is compared, and floor prepared by the present invention also has more preferable while having high intensity
Weatherability and anti-flammability, thus provide the present invention advantageous effects.
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express inaccuracy due to and not
The possible equivalent or son being presently considered are replaced, and these variations also should in the conceived case be interpreted by appended
Claim covers.
Claims (5)
1. high ferro high fire-retardance high durable rubber floor covering, is prepared by the raw material including following parts by weight：
；
Double amino-polyethyleneglycols modification hyperbranched poly pyrrole throats are prepared by following methods：
(1) the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride is prepared
1 mole of three acid anhydrides and appropriate metacresol are added in the three-necked flask being completely dried, stirs under inert gas protection,
After three acid anhydrides is completely dissolved, 0.5~1.2 mole of tetramine is added, after 30min is stirred at room temperature, is heated to 75~85 DEG C,
3.5~4.5h is reacted, then at 175~185 DEG C, reacts 3.5~4.5h；After reaction, room temperature is down to seal to get naphthalene anhydride
Hold hyperbranched poly pyrrole throat solution；
(2) double amino-polyethyleneglycols are prepared and modify hyperbranched poly pyrrole throat
In the terminated hyperbranched poly- pyrrole throat solution of naphthalene anhydride obtained toward step (2), 0.3~2 mole of double amino-polyethyleneglycols are added,
After 30min is stirred at room temperature under inert gas protection, 75~85 DEG C are heated to, reacts 3.5~4.5h, then at 175~185 DEG C
Under, react 3.5~4.5h；After reaction, it is down to room temperature, solution is poured into methanol, there is Precipitation；Repeatedly with methanol
After being filtered after washing removal solvent, the drying 22 at 50 DEG C~super to get the modification of double amino-polyethyleneglycols for 24 hours in vacuum drying oven
Branched poly- pyrrole throat；
Three acid anhydride is 1,3,5- tri- (4- naphthoxys -1,8- diacid) benzene, three acid anhydride；
The tetramine for being used to prepare double amino-polyethyleneglycols modification hyperbranched poly pyrrole throats is 3,3 ', 4,4 '-tetraminos two
Phenylate；
The filler is polybenzimidazoles coated silica compound particle, and the polybenzimidazoles coated silica is compound
Particle is prepared by following methods：
(1) preparation of amino-terminated polybenzimidazoles prepolymer
0.1 mole of tetramine is first dissolved in 1000 grams of polyphosphoric acids containing 85wt% phosphorus pentoxides, then by 0.05~
0.09 mole of diacid is added in reaction solution, after being reacted 15 hours at 220 DEG C, is down to room temperature, in precipitating to water, is then used
Ammonium hydroxide neutralizes, and filtering is dried in vacuo at 100 DEG C, obtains amino-terminated polybenzimidazoles prepolymer；
(2) preparation of silane-modified silica
Deionized water 100mL, KH- is added in the metal reaction container with blender, thermometer and condenser pipe of 1000mL
After 560 1g, it is slowly added into hydrophilic silicon oxides 20g under stiring, by being obtained by filtration after reacting 30 minutes at room temperature
Silane-modified silica；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL, 70 are added in the beaker of 300mL
After DEG C stirring and dissolving, above-mentioned silane-modified silica 1 5g is added and is warming up to 80 DEG C it is stirred 2 hours；It then will mixing
Object pours into deionized water, and filters, and filter cake is dried in vacuo 4 hours at 120 DEG C and obtains polybenzimidazoles coated silica
Compound particle；
The diacid is 5- amino isophthalic acids；
The tetramine for being used to prepare polybenzimidazoles coated silica compound particle is 3,3 '-diaminobenzidines.
2. high ferro as described in claim 1 high fire-retardance high durable rubber floor covering, wherein the average degree of polymerization of the PVC is
800~1500.
3. high ferro as described in claim 1 high fire-retardance high durable rubber floor covering, wherein in the EVA-g-MAH, MAH's
Grafting rate is 1%~6%.
4. high ferro as described in claim 1 high fire-retardance high durable rubber floor covering, wherein double amino-polyethyleneglycols are put down
Any one right in 44,89,112,135,180,226,453,1135 and 2271 of homopolymerization.
5. the high ferro preparation method of high fire-retardance high durable rubber floor covering, includes the following steps：
(1) the mixed machine of heat is added in Claims 1 to 4 any one of them raw material, is carried out under 110 DEG C of -130 DEG C of temperature conditions pre-
It is mixed, dry；
(2) it is sent into extruder after the material after drying being cooled to 40 DEG C -50 DEG C and carries out extrusion molding；
The barrel temperature of the extruder is followed successively by 195-205 DEG C, 185-195 DEG C, 175- along the direction of propulsion of the material
185℃、170-180℃；
The molding die temperature of the extruder, along the direction of propulsion of the material be followed successively by 155-165 DEG C, 160-170 DEG C,
165-175℃、175-185℃、195-205℃。
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