CN105860355A - High-speed rail high-flame retardant and high-weather resistant rubber floor and preparation method thereof - Google Patents
High-speed rail high-flame retardant and high-weather resistant rubber floor and preparation method thereof Download PDFInfo
- Publication number
- CN105860355A CN105860355A CN201610299212.3A CN201610299212A CN105860355A CN 105860355 A CN105860355 A CN 105860355A CN 201610299212 A CN201610299212 A CN 201610299212A CN 105860355 A CN105860355 A CN 105860355A
- Authority
- CN
- China
- Prior art keywords
- acid
- amino
- rubber floor
- floor covering
- weight portions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-speed rail high-flame retardant and high-weather resistant rubber floor. The high-speed rail high-flame retardant and high-weather resistant rubber floor is prepared by raw materials comprising PVC (polyvinyl chloride), EVA-g-MAH (ethylene vinyl acetale-g-maleic anhydride), natural rubber, butadiene styrene rubber, double-amino polyethylene glycol modified hyperbranched polypyrron, padding, barium/zinc complex stabilizer, KH-560, paraffin and stearic acid. The invention further discloses a preparation method of the high-speed rail high-flame retardant and high-weather resistant rubber floor.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly it relates to an high ferro high fire-retardance
High durable rubber floor covering and preparation method thereof.
Background technology
In recent years, along with developing rapidly of high-speed railway, increasing to the demand on high ferro floor.But,
Owing to using in high ferro, intensity, elasticity, weatherability and the anti-flammability on floor there is the highest requirement.
In prior art, generally use polyvinylchloride and the rubber bulk composition as floor, its intensity,
Deficiency is had, it is difficult to fully meet the demand of high ferro in elasticity, weatherability and anti-flammability.Additionally, in order to carry
High flame retardant, prior art typically adds inorganic combustion inhibitor to improve its performance, but inorganic material and high score
There is compatible problem in sub-material, easily reunites, but also can cause the decline of material mechanical performance, is difficult to obtain
Obtain the high ferro flooring material of excellent combination property.
Hence it is highly desirable to by formula and the improvement of production technology, possess high intensity, height obtaining one
The high ferro floor of the excellent combination property of elasticity, high-weatherability and high flame retardant.
Summary of the invention
In order to solve the problems referred to above, one aspect of the present invention provides a kind of high ferro high fire-retardance high durable rubber ground
Plate, is prepared from by the raw material including following weight portion:
Preferably, described high ferro high fire-retardance high durable rubber floor covering, the raw material including following weight portion prepare
Form:
In one embodiment, the average degree of polymerization of described PVC is 800～1500；Preferably, described
The average degree of polymerization of PVC is 930.
In one embodiment, in described EVA-g-MAH, the percent grafting of MAH is 1%～6%；Excellent
Selection of land, in described EVA-g-MAH, the percent grafting of MAH is 3%.
In one embodiment, described pair of amino-polyethyleneglycols modification hyperbranched poly pyrrole throat is prepared by following methods
Form:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
In the there-necked flask being completely dried, add three acid anhydrides of 1 mole and appropriate metacresol, protect at noble gas
Protect lower stirring, after three acid anhydrides are completely dissolved, add the tetramine of 0.5～1.2 mole, be stirred at room temperature 30min
After, it is heated to 75～85 DEG C, reacts 3.5～4.5h, then at 175～185 DEG C, react 3.5～4.5h；Instead
After should terminating, it is down to room temperature, obtains the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride；
(2) the double amino-polyethyleneglycols of preparation modifies hyperbranched poly pyrrole throat
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (2) obtains, add double ammonia of 0.3～2 mole
Base Polyethylene Glycol, after 30min being stirred at room temperature, is heated to 75～85 DEG C under inert gas shielding, reaction 3.5～
4.5h, then at 175～185 DEG C, react 3.5～4.5h；After reaction terminates, it is down to room temperature, solution is fallen
Enter in methanol, have Precipitation；Remove after filtering after solvent with methanol cyclic washing, in vacuum drying oven 50 DEG C
Lower drying 22～24h, obtains double amino-polyethyleneglycols and modifies hyperbranched poly pyrrole throat.
In one embodiment, described three acid anhydrides are 1,3,5-tri-(4-naphthoxy-1,8-diacid) benzene three acid anhydride.
In one embodiment, described for preparing described pair of amino-polyethyleneglycols modification hyperbranched poly pyrrole throat
Tetramine is selected from 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '
-tetramino diphenyl sulphone (DPS), 3,3 ', 4,4 '-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2,
Any one or more in 5,6-tetramino naphthalenes；Preferably, described tetramine is 3,3 ', 4,4 '-four ammonia
Yl diphenyl ether.
In one embodiment, the average degree of polymerization of described pair of amino-polyethyleneglycols selected from 44,89,112,
135, any one in 180,226,453,1135 and 2271；Preferably, the described pair of poly-second of amino
The average degree of polymerization of glycol is 226.
In one embodiment, described filler is polybenzimidazoles coated silica compound particle, and described
Polybenzimidazoles coated silica compound particle is prepared from 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 pentoxide, so
After the diacid of 0.05～0.09 mole is joined in reactant liquor, 220 DEG C reaction 15 hours after, be down to room temperature,
Precipitating, in water, then neutralizes with ammonia, filters, be vacuum dried, obtain amino-terminated polyphenyl at 100 DEG C
And imidazoles prepolymer；
(2) preparation of silane-modified silicon dioxide
Deionized water is added in the metal reaction container with agitator, thermometer and condensing tube of 1000mL
After 100mL, KH-560 1g, under agitation it is slowly added into hydrophilic silicon oxides 20g, reacts under room temperature
By being filtrated to get silane-modified silicon dioxide after 30 minutes；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide is added in the beaker of 300mL
150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified silica 1 5g and is warming up to 80 DEG C and stirs
Mix mixing 2 hours；Then pour the mixture in deionized water, and filter, filter cake is done in 120 DEG C of vacuum
Within dry 4 hours, obtain polybenzimidazoles coated silica compound particle.
In one embodiment, described diacid selected from adipic acid, 1,3-propanedicarboxylic acid, 1,5-pentanedicarboxylic acid., decanedioic acid, 12
Docosandioic acid, p-phthalic acid, M-phthalic acid, 2,2 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid and
Any one or more in 5-amino isophthalic acid；Preferably, described diacid is 5-amino isophthalic acid.
In one embodiment, the described tetramine for preparing polybenzimidazoles coated silica compound particle
Selected from 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-four
ADP sulfone, 3,3 ', 4,4 '-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2,5,
Any one or more in 6-tetramino naphthalene；Preferably, described tetramine is 3,3 '-diaminobenzidine.
Another aspect of the present invention provides the preparation method of described high ferro high fire-retardance high durable rubber floor covering, including
Following steps:
(1) described raw material is added the mixed machine of heat, carry out premixing, being dried under 110 DEG C of-130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 40 DEG C-50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195-205 DEG C,
185-195℃、175-185℃、170-180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155-165 DEG C,
160-170℃、165-175℃、175-185℃、195-205℃。
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Detailed description of the invention
Can be more easily understood with reference to the detailed description of preferred implementation of the invention below and the embodiment that includes
Present disclosure.Substantial amounts of term is referred to, these term quilts in description below and claims
It is defined as that there is following meanings.
" optional " or " optionally " refers to that subsequently described event or item may or may not occur, and should
Describe and include situation that event occurs and the situation that event does not occurs.
Approximation term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this
Particular number, also includes close to this quantity acceptable without causing repairing of the change of relevant basic function
Positive part.Accordingly, modify a numerical value with " about ", " about " etc., mean that to the invention is not restricted to this accurate
Numerical value.In some example, approximation term likely corresponds to detect the precision of the equipment of numerical value.Say in the application
In bright book and claims, scope limits and can combine and/or exchange, these models if not stated otherwise
Enclose and include all subranges contained therebetween.
Equivalent, concentration or other value or parameter with scope, preferred scope or a series of upper limit preferred value and under
During the Range Representation that limit preferred value limit is walked, this is appreciated that and specifically discloses by any range limit or preferred
All scopes that arbitrary pairing of value and any range lower limit or preferred value is formed, regardless of whether this scope is the most single
Solely disclose.Such as, when disclosing scope " l to 5 ", described scope should be interpreted as including scope " 1
To 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc..When numerical range is described in this article
Time, unless otherwise indicated, otherwise this scope is intended to include its end value and all integers within the range and mark.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or the quantity of component
Require (i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least
One, and the key element of singulative or component also include plural form, unless the obvious purport of described quantity refers to odd number
Form.
One aspect of the present invention provides a kind of high ferro high fire-retardance high durable rubber floor covering, by including following weight
The raw material of part is prepared from:
Preferably, described high ferro high fire-retardance high durable rubber floor covering, the raw material including following weight portion prepare
Form:
PVC
It is not particularly limited for the PVC of the application, can be commercially available any commercially produced product.
In one embodiment, the average degree of polymerization of described PVC is 800～1500；It is highly preferred that institute
The average degree of polymerization stating PVC is 930.
EVA-g-MAH
Maleic anhydride modified vinyl acetate co-polymer (EVA-g-MAH) in the application is not particularly limited, can
Think commercially available or experiment synthesis, such as, can use solution graft copolymerization and two kinds of methods synthesis of fusion-grafting.
In one embodiment, in described EVA-g-MAH, the percent grafting of MAH is 1%～6%；Excellent
Selection of land, in described EVA-g-MAH, the percent grafting of MAH is 3%.
Natural rubber
Natural rubber in the application is not particularly limited, and can be commercially available any commercially produced product.
Butadiene-styrene rubber
Butadiene-styrene rubber in the application is not particularly limited, and can be commercially available any commercially produced product.
Double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat
It is by double amino-polyethyleneglycols and naphthalene acid anhydride that double amino-polyethyleneglycols in the application modify hyperbranched poly pyrrole throat
The hyperbranched poly pyrrole throat reaction of end-blocking obtains.
In one embodiment, described pair of amino-polyethyleneglycols modification hyperbranched poly pyrrole throat is prepared by following methods
Form:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
In the there-necked flask being completely dried, add three acid anhydrides of 1 mole and appropriate metacresol, protect at noble gas
Protect lower stirring, after three acid anhydrides are completely dissolved, add the tetramine of 0.5～1.2 mole, be stirred at room temperature 30min
After, it is heated to 75～85 DEG C, reacts 3.5～4.5h, then at 175～185 DEG C, react 3.5～4.5h；Instead
After should terminating, it is down to room temperature, obtains the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride；
(2) the double amino-polyethyleneglycols of preparation modifies hyperbranched poly pyrrole throat
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (2) obtains, add double ammonia of 0.3～2 mole
Base Polyethylene Glycol, after 30min being stirred at room temperature, is heated to 75～85 DEG C under inert gas shielding, reaction 3.5～
4.5h, then at 175～185 DEG C, react 3.5～4.5h；After reaction terminates, it is down to room temperature, solution is fallen
Enter in methanol, have Precipitation；Remove after filtering after solvent with methanol cyclic washing, in vacuum drying oven 50 DEG C
Lower drying 22～24h, obtains double amino-polyethyleneglycols and modifies hyperbranched poly pyrrole throat.
In one is preferably carried out mode, described pair of amino-polyethyleneglycols modifies the preparation side of hyperbranched poly pyrrole throat
In method, the mol ratio of three acid anhydrides, tetramine and double amino-polyethyleneglycols is 1:1:1.
In one embodiment, described three acid anhydrides are 1,3,5-tri-(4-naphthoxy-1,8-diacid) benzene three acid anhydride.
In one embodiment, described 1,3,5-tri-(4-naphthoxy-1,8-diacid) benzene three acid anhydride is by with lower section
Method prepares:
In the 100mL three-necked bottle being furnished with nitrogen inlet, magnetic agitation, water knockout drum and reflux condensing tube, add
Enter 0.6305 gram of (5mmol) phloroglucinol, 8mL methanol, 0.60 gram of (15mmol) sodium hydroxide,
It is warming up to 100 DEG C, steams first alcohol and water, cool down after being evaporated, be cooled to room temperature, in reaction bulb, add 4.156
Gram (15mmol) 4-bromo-1,8-naphthalene acid anhydride, 10mL N-methylacetamide, it is warming up to 120 DEG C, by 15mL toluene
Instill reaction system to Dropping funnel, be warming up to 140 DEG C, react 4 hours, steam toluene, be warming up to 150 DEG C,
Continuing reaction 22 hours, after reaction terminates, system is cooled to room temperature.Then product is poured into 100mL acetone
In, filter after the solids washed with water separated out in system, vacuum drying, obtain crude product 2.58 grams.Gained
To crude product acetic anhydride carry out recrystallization, obtain pure products 1.53 grams, productivity 42.9%.
In one embodiment, described for preparing described pair of amino-polyethyleneglycols modification hyperbranched poly pyrrole throat
Tetramine is selected from 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '
-tetramino diphenyl sulphone (DPS), 3,3 ', 4,4 '-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2,
Any one or more in 5,6-tetramino naphthalenes；Preferably, described tetramine is 3,3 ', 4,4 '-four ammonia
Yl diphenyl ether.
In one embodiment, the average degree of polymerization of described pair of amino-polyethyleneglycols selected from 44,89,112,
135, any one in 180,226,453,1135 and 2271；Preferably, the described pair of poly-second of amino
The average degree of polymerization of glycol is 226.
Poly-pyrrole throat has the weatherability of excellence, higher intensity and good fire resistance, but general gathering
Pyrrole throat does not have good processing characteristics, and difficult the most compatible with PVC, by double amino-polyethyleneglycols
Modify and select dissaving structure, the compatibility and processing problems can be efficiently solved, additionally, a large amount of ammonia
The existence of base, can be greatly improved mechanical strength as the crosslinking points of system, thus provides having of the present invention
Benefit technique effect.
Filler
Filler in the application is not particularly limited, and can be commercially available any commercially produced product or synthesis obtains.
Such as calcium carbonate, hydrophilic silicon oxides or polybenzimidazoles coated silica compound particle, but preferably, institute
Stating filler is polybenzimidazoles coated silica compound particle, and described polybenzimidazoles coated silica is multiple
Close particle to be prepared from 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 pentoxide, so
After the diacid of 0.05～0.09 mole is joined in reactant liquor, 220 DEG C reaction 15 hours after, be down to room temperature,
Precipitating, in water, then neutralizes with ammonia, filters, be vacuum dried, obtain amino-terminated polyphenyl at 100 DEG C
And imidazoles prepolymer；
(2) preparation of silane-modified silicon dioxide
Deionized water is added in the metal reaction container with agitator, thermometer and condensing tube of 1000mL
After 100mL, KH-560 1g, under agitation it is slowly added into hydrophilic silicon oxides 20g, reacts under room temperature
By being filtrated to get silane-modified silicon dioxide after 30 minutes；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide is added in the beaker of 300mL
150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified silica 1 5g and is warming up to 80 DEG C and stirs
Mix mixing 2 hours；Then pour the mixture in deionized water, and filter, filter cake is done in 120 DEG C of vacuum
Within dry 4 hours, obtain polybenzimidazoles coated silica compound particle.
In one is preferably carried out mode, tetramine is 1:0.9 with the mol ratio of diacid.
In one embodiment, described diacid selected from adipic acid, 1,3-propanedicarboxylic acid, 1,5-pentanedicarboxylic acid., decanedioic acid, 12
Docosandioic acid, p-phthalic acid, M-phthalic acid, 2,2 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid and
Any one or more in 5-amino isophthalic acid；Preferably, described diacid is 5-amino isophthalic acid.
In one embodiment, the described tetramine for preparing polybenzimidazoles coated silica compound particle
Selected from 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-four
ADP sulfone, 3,3 ', 4,4 '-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2,5,
Any one or more in 6-tetramino naphthalene；Preferably, described tetramine is 3,3 '-diaminobenzidine.
Polybenzimidazoles can effective quencher free radical, to improve the ageing-resistant performance of system, in addition polybenzimidazoles
Also it is extraordinary fire proofing, adds by the way of compound with silicon dioxide, both solved polybenzimidazoles
Compatible problem with PVC, it is possible to ensure that silicon dioxide will not be reunited, be well dispersed in system, thus
Provide the Advantageous Effects of the present invention.
Barium/zinc composite stabilizer
Barium/zinc composite stabilizer in the application is not particularly limited, and can be commercially available any commercially produced product.
KH-560
Epoxy silane coupling agent KH-560 in the application is not particularly limited, and can be commercially available any business
Change product.
Paraffin
Paraffin in the application is not particularly limited, and can be commercially available any commercially produced product.
Stearic acid
Stearic acid in the application is not particularly limited, and can be commercially available any commercially produced product.
Another aspect of the present invention provides the preparation method of described high ferro high fire-retardance high durable rubber floor covering, including
Following steps:
(1) described raw material is added the mixed machine of heat, carry out premixing, being dried under 110 DEG C of-130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 40 DEG C-50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195-205 DEG C,
185-195℃、175-185℃、170-180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155-165 DEG C,
160-170℃、165-175℃、175-185℃、195-205℃。
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example
It is served only for that the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, this field
Some nonessential improvement and adjustment that professional and technical personnel makes according to the content of the invention described above, still fall within this
The protection domain of invention.
It addition, illustrate without other, raw materials used is all commercially available, and number used by following material is
Weight portion.
Raw material:
All tetramines, diacid are purchased from CTI, SigmaAldrich, AlfaAesar or SCRC, and directly
Use, it is not necessary to be further purified.Hydrophilic silicon oxides (dry vapor silicon dioxide), purchased from Shenyang chemical industry stock
Part company limited.KH-560, calcium carbonate are purchased from Chemical Reagent Co., Ltd., Sinopharm Group.Other raw materials are all purchased
From Aladdin reagent company limited.
A1:PVC (average degree of polymerization is 800)
A2:PVC (average degree of polymerization is 1500)
A3:PVC (average degree of polymerization is 930)
B1:EVA-g-MAH (MAH percent grafting is 1%)
B2:EVA-g-MAH (MAH percent grafting is 6%)
B3:EVA-g-MAH (MAH percent grafting is 3%)
C1: natural rubber
D1: butadiene-styrene rubber
E1: double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat, following methods be prepared from:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
1,3,5-tri-(4-naphthoxy-1,8-diacid) benzene of 1 mole is added in the there-necked flask being completely dried
Three acid anhydrides and 2000ml metacresol, stir under nitrogen protection, after three acid anhydrides are completely dissolved, adds 0.5 mole
3,3 '-diaminobenzidine, after being stirred at room temperature 30min, be heated to 85 DEG C, react 3.5h, then
At 185 DEG C, react 4.5h；After reaction terminates, it is down to room temperature, obtains the terminated hyperbranched poly-pyrrole throat of naphthalene acid anhydride molten
Liquid；
(2) the double amino-polyethyleneglycols of preparation modifies hyperbranched poly pyrrole throat
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (2) obtains, the double amino adding 2 moles gather
Ethylene glycol, after 30min being stirred at room temperature under nitrogen protection, is heated to 85 DEG C, reacts 4.5h, then at 185 DEG C
Under, react 4.5h；After reaction terminates, it is down to room temperature, solution is poured in methanol, has Precipitation；Use first
After alcohol cyclic washing filters after removing solvent, in vacuum drying oven, at 50 DEG C, dry 24h, obtain double poly-second of amino
Glycol modifies hyperbranched poly pyrrole throat.
E2: double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat, following methods be prepared from:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
1,3,5-tri-(4-naphthoxy-1,8-diacid) benzene of 1 mole is added in the there-necked flask being completely dried
Three acid anhydrides and 2000ml metacresol, stir under nitrogen protection, after three acid anhydrides are completely dissolved, adds 1 mole
3,3 '-diaminobenzidine, after being stirred at room temperature 30min, it is heated to 85 DEG C, reaction 3.5h, then
At 185 DEG C, react 4.5h；After reaction terminates, it is down to room temperature, obtains the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride；
(2) the double amino-polyethyleneglycols of preparation modifies hyperbranched poly pyrrole throat
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (2) obtains, the double amino adding 1 mole gather
Ethylene glycol, after 30min being stirred at room temperature under nitrogen protection, is heated to 85 DEG C, reacts 4.5h, then at 185 DEG C
Under, react 4.5h；After reaction terminates, it is down to room temperature, solution is poured in methanol, has Precipitation；Use first
After alcohol cyclic washing filters after removing solvent, in vacuum drying oven, at 50 DEG C, dry 24h, obtain double poly-second of amino
Glycol modifies hyperbranched poly pyrrole throat.
E3:
Double amino-polyethyleneglycols modify hyperbranched poly pyrrole throat, following methods be prepared from:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
1,3,5-tri-(4-naphthoxy-1,8-diacid) benzene of 1 mole is added in the there-necked flask being completely dried
Three acid anhydrides and 2000ml metacresol, stir under nitrogen protection, after three acid anhydrides are completely dissolved, adds 1 mole
3,3 ', 4,4 '-tetramino diphenyl ether, after being stirred at room temperature 30min, it is heated to 85 DEG C, reacts 3.5h,
Again at 185 DEG C, react 4.5h；After reaction terminates, it is down to room temperature, obtains the terminated hyperbranched poly-pyrrole throat of naphthalene acid anhydride
Solution；
(2) the double amino-polyethyleneglycols of preparation modifies hyperbranched poly pyrrole throat
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (2) obtains, the double amino adding 1 mole gather
Ethylene glycol, after 30min being stirred at room temperature under nitrogen protection, is heated to 85 DEG C, reacts 4.5h, then at 185 DEG C
Under, react 4.5h；After reaction terminates, it is down to room temperature, solution is poured in methanol, has Precipitation；Use first
After alcohol cyclic washing filters after removing solvent, in vacuum drying oven, at 50 DEG C, dry 24h, obtain double poly-second of amino
Glycol modifies hyperbranched poly pyrrole throat.
F1: calcium carbonate
F2: hydrophilic silicon oxides (dry vapor silicon dioxide)
F3: polybenzimidazoles coated silica compound particle is prepared from by following methods:
(1) preparation of amino-terminated polybenzimidazoles prepolymer
By 0.1 mole 3,3 ', 4,4 '-tetramino diphenyl ether is first dissolved in containing 85wt% phosphorus pentoxide
In 1000 grams of polyphosphoric acids, then the p-phthalic acid of 0.05 mole is joined in reactant liquor, at 220 DEG C
After reacting 15 hours, it is down to room temperature, in precipitating to water, then neutralizes with ammonia, filter, at 100 DEG C
Vacuum drying, obtains amino-terminated polybenzimidazoles prepolymer；
(2) preparation of silane-modified silicon dioxide
Deionized water is added in the metal reaction container with agitator, thermometer and condensing tube of 1000mL
After 100mL, KH-560 1g, under agitation it is slowly added into hydrophilic silicon oxides 20g, reacts under room temperature
By being filtrated to get silane-modified silicon dioxide after 30 minutes；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide is added in the beaker of 300mL
150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified silica 1 5g and is warming up to 80 DEG C and stirs
Mix mixing 2 hours；Then pour the mixture in deionized water, and filter, filter cake is done in 120 DEG C of vacuum
Within dry 4 hours, obtain polybenzimidazoles coated silica compound particle.
F4: polybenzimidazoles coated silica compound particle is prepared from by following methods:
(1) preparation of amino-terminated polybenzimidazoles prepolymer
By 0.1 mole 3,3 '-diaminobenzidine is first dissolved in 1000 containing 85wt% phosphorus pentoxide
In gram polyphosphoric acids, then the 5-amino isophthalic acid of 0.09 mole is joined in reactant liquor, at 220 DEG C
After reacting 15 hours, it is down to room temperature, in precipitating to water, then neutralizes with ammonia, filter, at 100 DEG C
Vacuum drying, obtains amino-terminated polybenzimidazoles prepolymer；
(2) preparation of silane-modified silicon dioxide
Deionized water is added in the metal reaction container with agitator, thermometer and condensing tube of 1000mL
After 100mL, KH-560 1g, under agitation it is slowly added into hydrophilic silicon oxides 20g, reacts under room temperature
By being filtrated to get silane-modified silicon dioxide after 30 minutes；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide is added in the beaker of 300mL
150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified silica 1 5g and is warming up to 80 DEG C and stirs
Mix mixing 2 hours；Then pour the mixture in deionized water, and filter, filter cake is done in 120 DEG C of vacuum
Within dry 4 hours, obtain polybenzimidazoles coated silica compound particle.
G1: barium/zinc composite stabilizer
H1:KH-560
I1: paraffin
J1: stearic acid
Embodiment 1
By the A1 of 100 weight portions, the B1 of 20 weight portions, the C1 of 10 weight portions, the D1 of 5 weight portions, 5
The E1 of weight portion, the F1 of 10 weight portions, the G1 of 1 weight portion, the H1 of 2 weight portions, the I1 of 1 weight portion
And 0.5 the J1 of weight portion add the mixed machine of heat, carry out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Embodiment 2
By the A2 of 100 weight portions, the B2 of 50 weight portions, the C1 of 25 weight portions, the D1 of 8 weight portions, 20
The E1 of weight portion, the F1 of 50 weight portions, the G1 of 40 weight portions, the H1 of 8 weight portions, the I1 of 5 weight portions
And 2 the J1 of weight portion add the mixed machine of heat, carry out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Embodiment 3
By the A3 of 100 weight portions, the B3 of 25 weight portions, the C1 of 30 weight portions, the D1 of 10 weight portions,
The E1 of 15 weight portions, the F1 of 40 weight portions, the G1 of 20 weight portions, the H1 of 7 weight portions, 4 weight portions
The J1 of I1 and 1 weight portion adds the mixed machine of heat, carries out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Embodiment 4
By the A3 of 100 weight portions, the B3 of 25 weight portions, the C1 of 30 weight portions, the D1 of 10 weight portions,
The E2 of 15 weight portions, the F1 of 40 weight portions, the G1 of 20 weight portions, the H1 of 7 weight portions, 4 weight portions
The J1 of I1 and 1 weight portion adds the mixed machine of heat, carries out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Embodiment 5
By the A3 of 100 weight portions, the B3 of 25 weight portions, the C1 of 30 weight portions, the D1 of 10 weight portions,
The E3 of 15 weight portions, the F1 of 40 weight portions, the G1 of 20 weight portions, the H1 of 7 weight portions, 4 weight portions
The J1 of I1 and 1 weight portion adds the mixed machine of heat, carries out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Embodiment 6
By the A3 of 100 weight portions, the B3 of 25 weight portions, the C1 of 30 weight portions, the D1 of 10 weight portions,
The E3 of 15 weight portions, the F2 of 40 weight portions, the G1 of 20 weight portions, the H1 of 7 weight portions, 4 weight portions
The J1 of I1 and 1 weight portion adds the mixed machine of heat, carries out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Embodiment 7
By the A3 of 100 weight portions, the B3 of 25 weight portions, the C1 of 30 weight portions, the D1 of 10 weight portions,
The E3 of 15 weight portions, the F3 of 40 weight portions, the G1 of 20 weight portions, the H1 of 7 weight portions, 4 weight portions
The J1 of I1 and 1 weight portion adds the mixed machine of heat, carries out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Embodiment 8
By the A3 of 100 weight portions, the B3 of 25 weight portions, the C1 of 30 weight portions, the D1 of 10 weight portions,
The E3 of 15 weight portions, the F4 of 40 weight portions, the G1 of 20 weight portions, the H1 of 7 weight portions, 4 weight portions
The J1 of I1 and 1 weight portion adds the mixed machine of heat, carries out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Comparative example 1
By the A3 of 100 weight portions, the B3 of 25 weight portions, the C1 of 30 weight portions, the D1 of 10 weight portions,
The F4 of 40 weight portions, the G1 of 20 weight portions, the H1 of 7 weight portions, the I1 of 4 weight portions and 1 weight portion
J1 add the mixed machine of heat, carry out premixing, being dried under 130 DEG C of temperature conditionss；
(2) send into extruder after dried material being cooled to 50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195 DEG C, 195 DEG C, 185 DEG C,
180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155 DEG C, 160 DEG C,
165℃、185℃、195℃。
Method of testing
Hot strength and elongation at break: according to GB/T 1040-92 standard testing.
Weatherability is tested: in the sodium hydrate aqueous solution of the 1mol/L that gained floor is immersed in 50 DEG C, 24 is little
Its loss of tensile strength rate is tested time after；In the aqueous sulfuric acid of the 1mol/L that gained floor is immersed in 50 DEG C,
Its loss of tensile strength rate is tested after 24 hours.
Fire resistance: according to GB/T 2046 standard test oxygen index (OI)
Test result is shown in Table 1.
Table 1
Data above is it can be seen that modify hyperbranched poly pyrrole throat and polyphenyl also with not using double amino-polyethyleneglycols
The product of imidazoles coated silica compound particle is compared, floor prepared by the present invention while possessing high intensity,
Also there is more preferable weatherability and anti-flammability, be thus provided that the Advantageous Effects of the present invention.
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended right
Require to be intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only according to all
The explanation of the embodiment of the selection of the combination of possible embodiment.Therefore, the purpose of applicant is appended power
Profit requires the selectional restriction of example inventive feature not being described.And progressive in science and technology will be formed by
The possible equivalent or the son that are not presently considered in the inaccurate reason of language performance are replaced, and these become
Change and also should be interpreted in the conceived case to be covered by appended claim.
Claims (10)
1. high ferro high fire-retardance high durable rubber floor covering, is prepared from by the raw material including following weight portion:
2. high ferro high fire-retardance high durable rubber floor covering as claimed in claim 1, wherein, described PVC's
Average degree of polymerization is 800～1500.
3. high ferro high fire-retardance high durable rubber floor covering as claimed in claim 1, wherein, described
In EVA-g-MAH, the percent grafting of MAH is 1%～6%.
4. high ferro high fire-retardance high durable rubber floor covering as claimed in claim 1, wherein, described pair of amino
Polyethyleneglycol modified hyperbranched poly pyrrole throat is prepared from by following methods:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
In the there-necked flask being completely dried, add three acid anhydrides of 1 mole and appropriate metacresol, protect at noble gas
Protect lower stirring, after three acid anhydrides are completely dissolved, add the tetramine of 0.5～1.2 mole, be stirred at room temperature 30min
After, it is heated to 75～85 DEG C, reacts 3.5～4.5h, then at 175～185 DEG C, react 3.5～4.5h；Instead
After should terminating, it is down to room temperature, obtains the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride；
(2) the double amino-polyethyleneglycols of preparation modifies hyperbranched poly pyrrole throat
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (2) obtains, add double ammonia of 0.3～2 mole
Base Polyethylene Glycol, after 30min being stirred at room temperature, is heated to 75～85 DEG C under inert gas shielding, reaction 3.5～
4.5h, then at 175～185 DEG C, react 3.5～4.5h；After reaction terminates, it is down to room temperature, solution is fallen
Enter in methanol, have Precipitation；Remove after filtering after solvent with methanol cyclic washing, in vacuum drying oven 50 DEG C
Lower drying 22～24h, obtains double amino-polyethyleneglycols and modifies hyperbranched poly pyrrole throat.
5. high ferro high fire-retardance high durable rubber floor covering as claimed in claim 4, wherein, described three acid anhydrides are
1,3,5-tri-(4-naphthoxy-1,8-diacid) benzene three acid anhydride.
6. high ferro high fire-retardance high durable rubber floor covering as claimed in claim 4, wherein, described pair of amino
The average degree of polymerization of Polyethylene Glycol is selected from 44,89,112,135,180,226,453,1135 and 2271
In any one.
7. high ferro high fire-retardance high durable rubber floor covering as claimed in claim 1, wherein, described filler is
Polybenzimidazoles coated silica compound particle, and described polybenzimidazoles coated silica compound particle by
Following methods is prepared from:
(1) preparation of amino-terminated polybenzimidazoles prepolymer
0.1 mole of tetramine is first dissolved in 1000 grams of polyphosphoric acids containing 85wt% phosphorus pentoxide, so
After the diacid of 0.05～0.09 mole is joined in reactant liquor, 220 DEG C reaction 15 hours after, be down to room temperature,
Precipitating, in water, then neutralizes with ammonia, filters, be vacuum dried, obtain amino-terminated polyphenyl at 100 DEG C
And imidazoles prepolymer；
(2) preparation of silane-modified silicon dioxide
Deionized water is added in the metal reaction container with agitator, thermometer and condensing tube of 1000mL
After 100mL, KH-560 1g, under agitation it is slowly added into hydrophilic silicon oxides 20g, reacts under room temperature
By being filtrated to get silane-modified silicon dioxide after 30 minutes；
(3) preparation of polybenzimidazoles coated silica compound particle
Above-mentioned amino-terminated polybenzimidazoles prepolymer 1.8g, dimethyl sulfoxide is added in the beaker of 300mL
150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified silica 1 5g and is warming up to 80 DEG C and stirs
Mix mixing 2 hours；Then pour the mixture in deionized water, and filter, filter cake is done in 120 DEG C of vacuum
Within dry 4 hours, obtain polybenzimidazoles coated silica compound particle.
8. high ferro high fire-retardance high durable rubber floor covering as claimed in claim 7, wherein, described diacid selects
From adipic acid, 1,3-propanedicarboxylic acid, 1,5-pentanedicarboxylic acid., decanedioic acid, dodecanedioic acid, p-phthalic acid, M-phthalic acid,
2,2 '-biphenyl dicarboxylic acid, 4, in 4 '-biphenyl dicarboxylic acid and 5-amino isophthalic acid any one or many
Kind.
9. the high fire-retardance high durable rubber floor covering of the high ferro as described in claim 4 or 7, wherein, described four
Amine is selected from 3,3 '-diaminobenzidine, 3,3 ', 4, and 4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-
Tetramino diphenyl sulphone (DPS), 3,3 ', 4,4 '-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2,
Any one or more in 5,6-tetramino naphthalenes.
10. the high ferro preparation method of high fire-retardance high durable rubber floor covering, comprises the following steps:
(1) raw material described in any one of claim 1～9 is added the mixed machine of heat, 110 DEG C of-130 DEG C of temperature strip
Carry out under part premixing, being dried；
(2) send into extruder after dried material being cooled to 40 DEG C-50 DEG C and carry out extrusion molding；
The barrel temperature of described extruder, the direction of propulsion along described material be followed successively by 195-205 DEG C,
185-195℃、175-185℃、170-180℃；
The mould temperature of described extruder, the direction of propulsion along described material be followed successively by 155-165 DEG C,
160-170℃、165-175℃、175-185℃、195-205℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610299212.3A CN105860355B (en) | 2016-05-06 | 2016-05-06 | High ferro high fire-retardance high durable rubber floor covering and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610299212.3A CN105860355B (en) | 2016-05-06 | 2016-05-06 | High ferro high fire-retardance high durable rubber floor covering and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105860355A true CN105860355A (en) | 2016-08-17 |
| CN105860355B CN105860355B (en) | 2018-08-24 |
Family
ID=56631325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610299212.3A Active CN105860355B (en) | 2016-05-06 | 2016-05-06 | High ferro high fire-retardance high durable rubber floor covering and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105860355B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543597A (en) * | 2016-11-24 | 2017-03-29 | 安徽省天乐塑业有限公司 | A kind of fire resistant elastomeric material and preparation method thereof |
| CN107674268A (en) * | 2017-10-11 | 2018-02-09 | 陕西秦力橡胶有限责任公司 | A kind of artificial granite line rubber floor covering and its production method |
| CN108084599A (en) * | 2017-12-04 | 2018-05-29 | 安吉天则塑业有限公司 | A kind of method for making PVC plastic adhesive floor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382400A (en) * | 2011-10-17 | 2012-03-21 | 常熟市威腾进出口有限公司 | Flame retardant polyvinyl chloride composition and preparation method |
-
2016
- 2016-05-06 CN CN201610299212.3A patent/CN105860355B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382400A (en) * | 2011-10-17 | 2012-03-21 | 常熟市威腾进出口有限公司 | Flame retardant polyvinyl chloride composition and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 周惠久主编: "《新材料辞典》", 30 December 1996, 上海科学技术文献出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543597A (en) * | 2016-11-24 | 2017-03-29 | 安徽省天乐塑业有限公司 | A kind of fire resistant elastomeric material and preparation method thereof |
| CN107674268A (en) * | 2017-10-11 | 2018-02-09 | 陕西秦力橡胶有限责任公司 | A kind of artificial granite line rubber floor covering and its production method |
| CN107674268B (en) * | 2017-10-11 | 2019-11-22 | 陕西秦力橡胶有限责任公司 | A kind of artificial granite line rubber floor covering and its production method |
| CN108084599A (en) * | 2017-12-04 | 2018-05-29 | 安吉天则塑业有限公司 | A kind of method for making PVC plastic adhesive floor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105860355B (en) | 2018-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105255089B (en) | High fire-retardance high abrasion Halogen cross-linked polyolefin cable insulating materials and preparation method thereof | |
| WO2018014443A1 (en) | Halogen-free phosphorus-containing silicon flame retardant, flame retardant transparent polycarbonate material, and preparation and use thereof | |
| CN105860355A (en) | High-speed rail high-flame retardant and high-weather resistant rubber floor and preparation method thereof | |
| CN108359084B (en) | High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzimide structure and preparation method thereof | |
| CN105255090B (en) | Use the composition and high-strength halogen-free flame-retardant insulating material therefrom of SEBS reclaimed materials | |
| JP2001503792A (en) | Plasticized polymer composition | |
| DE1595781C3 (en) | Process for the production of high molecular weight, thermoplastic polyesters. Eliminated from: 1445384 | |
| CN108530887A (en) | A kind of high heat-resisting, high intensity semiaromatic polyamide composition/polyester alloy material and its preparation method and application | |
| CN105968805A (en) | Modified material capable of replacing metal and preparation method thereof | |
| CN112457478B (en) | Boric acid modified unsaturated polyester and preparation method thereof | |
| CN105820475B (en) | The heat-insulated mute floor board of bullet train | |
| JP2947094B2 (en) | Method for producing high molecular weight polyamide-imide resin | |
| CN105505295B (en) | Flame retardant type silicone sealant and preparation method thereof | |
| CN114854173A (en) | Composite epoxy resin composition and preparation method thereof | |
| CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
| CN108219427A (en) | Biological grade transparent flame-retardant polycarbonate compound and preparation method thereof | |
| JP2001172238A (en) | Aromatic diamine/aromatic dicarboxylic acid salt and method for producing the same | |
| JPH0718172A (en) | Molding material based on polyarylene ether | |
| CN105153417A (en) | Halogen-free flame-retardant high-temperature nylon | |
| CN105315603A (en) | Flame-retardant thermoplastic elastomer composition | |
| CN118027458B (en) | Carbon fiber reinforced polypropylene composite material and preparation method thereof | |
| JPH031345B2 (en) | ||
| JPS5910697B2 (en) | Reinforced flame-retardant resin composition with improved electrical properties | |
| JPH01207322A (en) | Polycarbonamide of bis(2-(4-carboxyphenyl) hexafluoroisopropyl)diphenyl ether | |
| JP2018109134A (en) | Catalyst, method for producing the same, composition for polyester production containing the same, and method for producing polyester using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |