CN106478926A - A kind of compositionss and preparation method thereof and the application in fire proofing field - Google Patents
A kind of compositionss and preparation method thereof and the application in fire proofing field Download PDFInfo
- Publication number
- CN106478926A CN106478926A CN201610967065.2A CN201610967065A CN106478926A CN 106478926 A CN106478926 A CN 106478926A CN 201610967065 A CN201610967065 A CN 201610967065A CN 106478926 A CN106478926 A CN 106478926A
- Authority
- CN
- China
- Prior art keywords
- compositionss
- product
- poly
- propylene carbonate
- glycol
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to fine polymer Material Field, more particularly, to a kind of compositionss and preparation method thereof and the application in fire proofing field.The invention provides a kind of compositionss, the raw material of described compositionss includes：Poly (propylene carbonate) glycol, diisocyanate, chain extender, catalyst, polymerization inhibitor and halogen-free flame retardants.Present invention also offers a kind of preparation method of above-mentioned composition, present invention also offers a kind of application in fire proofing field for the product that obtains of above-mentioned composition or above-mentioned preparation method.In the technical scheme that the present invention provides, the addition of fire retardant is few, and one of the material of preparing being used is to be obtained with carbon dioxide for raw material, and cost is than less expensive；Meanwhile, without there being halogen, do not result in secondary pollution, meet the requirement of today's society environmental protection sustainable development.Through experimental tests can obtain, the product that the technical scheme that the present invention provides is obtained, and fire resistance is good, and high mechanical strength has good weatherability, wearability and oil resistivity.
Description
Technical field
The invention belongs to fine polymer Material Field, more particularly, to a kind of compositionss and preparation method thereof with fire-retardant material
The application in material field.
Background technology
At present, most cable material is mainly polrvinyl chloride (PVC) and prepares for raw material, PVC excellent flame retardancy, raw
Produce low cost, the use requirement of electric wire product can be met, be therefore widely used in the manufacture of various cables.But, PVC
There are some problems, such as loss of properties on aging, aging after be easy to leak electricity, produce potential safety hazard；Meanwhile, PVC is in high temperature
The lower easily poisonous hydrogen chloride of release, causes secondary pollution.Therefore, halogen CABLE MATERIALS is usually prohibited from using.Meanwhile, PVC is also
There is wearability, folding resistance difference problem.
In order to solve the drawbacks described above of PVC, develop multiple PVC substitutes, such as：TPE and TPU etc..However, prior art
In, the fire resistance of TPE is poor, for realizing the flame retardant effect of TPE, need to add a large amount of fire retardants, not only cause material cost
Rise, and product weatherability, wearability, oil resistivity and mechanical strength etc. can be led to significantly to decline.Polyester-type TPU's is strong
Degree is high, it is fire-retardant easily to realize, and retardant load level is typically relatively low, and the addition of fire retardant is little on properties of product impact, but
Polyester-type TPU anti-hydrolytic performance is poor, with it for the cable range of raw material preparation limited by.
Therefore, develop a kind of good physical properties, there are good hydrolysis, wear-resisting, weather-proof and fire resistance
Cable material, for solving in prior art, the technology that cable material poor flame retardant properties, manufacturing cost are high and performance is low lacks
Fall into, become those skilled in the art's problem demanding prompt solution.
Content of the invention
In view of this, the invention provides a kind of compositionss and preparation method thereof and the application in fire proofing field, use
In solution prior art, the technological deficiency that cable material poor flame retardant properties, manufacturing cost are high and performance is low.The present invention provides
Technical scheme be obtained product, good physical properties, there is good hydrolysis, wear-resisting, weather-proof and fire resistance.
The invention provides a kind of compositionss, the raw material of described compositionss includes：Poly (propylene carbonate) glycol, two Carbimide .s
Ester, chain extender, catalyst, polymerization inhibitor and halogen-free flame retardants.
Preferably, in terms of mass parts, the raw material of described compositionss includes：100 parts of poly (propylene carbonate) glycol, two Carbimide .s
60～90 parts of ester, 8～12 parts of chain extender, 0.01～1 part of catalyst, 0.1～1 part of polymerization inhibitor and 5～15 parts of halogen-free flame retardants.
Preferably, the preparation method of described poly (propylene carbonate) glycol is：With carbon dioxide as initiation material, in initiator
In the presence of catalyst, become to be obtained with epoxypropane copolymerization；
The molecular weight of described poly (propylene carbonate) glycol is 1000～8000, the hydroxyl official of described poly (propylene carbonate) glycol
Energy degree is 2～6, and in described poly (propylene carbonate) glycol molecules, the mole fraction of carbonate group is 0.25～0.45.
Preferably, the molecular weight of described poly (propylene carbonate) glycol is 2000～4000, described poly (propylene carbonate) glycol
Hydroxy functionality be 2～3, in described poly (propylene carbonate) glycol molecules the mole fraction of carbonate group be 0.30～
0.40.
Preferably, described diisocyanate is selected from：Toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and liquefaction two
One or more of methylenebis phenyl isocyanate.
Preferably, described chain extender is selected from：One or more of ethylene glycol, BDO and diglycol.
Preferably, described catalyst is selected from：One of stannous octoate, stannous iso caprylate, dibutyl tin laurate or
Multiple.
Preferably, described halogen-free flame retardants is：Methyl-phosphoric acid dimethyl ester and/or bisphenol-A are double (diphenyl phosphoester)；
Described polymerization inhibitor is selected from：Methyl-phosphoric acid dimethyl ester and/or bisphenol-A are double (diphenyl phosphoester).
Present invention also offers a kind of preparation method including the compositionss described in any of the above one, described preparation method
For：
Step one, by after poly (propylene carbonate) diol dehydratase, mix with polymerization inhibitor, diisocyanate and catalyst, stirring
After cool down, obtain the first product；
Step 2, by after the fire retardant after dehydration and chain extender and described first product, vacuum outgass are reacted, and obtain the second product
Thing；
Step 3, described second product are poured in grinding tool, sequentially pass through solidification, ripening, after standing, broken pelletize, obtain product
Product.
Preferably, the temperature of stirring described in step one is 60～80 DEG C, and the time of stirring described in step one is 2～3h, step
Described in rapid one, the temperature of cooling is 40～50 DEG C；
Described in step 2, the time of vacuum outgass reaction is 5～10min；
The time of solidification described in step 3 is 12h, and described in step 3, the temperature of solidification is 80 DEG C, ripening described in step 3
Time is 12h, and curing temperature described in step 3 is 100 DEG C, and the time of standing described in step 3 is 24h, stands described in step 3
Temperature be room temperature.
Present invention also offers a kind of system described in any one for the compositionss including described in any of the above one or more
The product that Preparation Method obtains is in the application in fire proofing field.
In sum, the invention provides a kind of compositionss, the raw material of described compositionss includes：Poly (propylene carbonate) two
Alcohol, diisocyanate, chain extender, catalyst, polymerization inhibitor and halogen-free flame retardants.Present invention also offers a kind of above-mentioned composition
Preparation method, present invention also offers the product that a kind of above-mentioned composition or above-mentioned preparation method obtain is in fire proofing field
Application.In the technical scheme that the present invention provides, the addition of fire retardant is few, and one of the material of preparing being used is with carbon dioxide
It is obtained for raw material, cost is than less expensive；Meanwhile, without there being halogen, do not result in secondary pollution, meet today's society ring
Protect the requirement of sustainable development.Through experimental tests can obtain, the product that the technical scheme that the present invention provides is obtained, and fire resistance is good
Good, high mechanical strength, there is good weatherability, wearability and oil resistivity.
Specific embodiment
The invention provides a kind of compositionss and preparation method thereof and the application in fire proofing field, existing for solving
In technology, the technological deficiency that cable material poor flame retardant properties, manufacturing cost are high and performance is low.The technical scheme that the present invention provides
Prepared product, good physical properties, there is good hydrolysis, wear-resisting, weather-proof and fire resistance.
The enforcement it is clear that described will be clearly and completely described to the technical scheme in the embodiment of the present invention below
Example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of not making creative work, broadly falls into the model of present invention protection
Enclose.
In order to the present invention is described in more detail, a kind of compositionss present invention being provided with reference to embodiment and its preparation side
Method and the application in fire proofing field, are specifically described.
Embodiment 1
Weigh 100g poly (propylene carbonate) glycol, in the glass reaction kettle with vacuum extractor, 120 DEG C of evacuation take off
Water 2 hours, after dropping to room temperature, is mixed with 0.01g polymerization inhibitor, 60g diisocyanate and 0.02g catalyst, anti-in 80 DEG C of stirrings
After answering 3h, it is cooled to 40 DEG C, obtain the first product 1.
Weigh 5g fire retardant and 8.5g chain extender, in the glass reaction kettle with vacuum extractor, after evacuation dehydration,
After mixing with the first product 1,5min is reacted in vacuum outgass, obtains the second product 1.
Second product 1 is poured in preheated grinding tool immediately, is solidified after 12h with 80 DEG C in an oven, then in 100 DEG C of ripenings
12h, broken pelletize after room temperature standing 24h, obtain product 1.
In the present embodiment, poly (propylene carbonate) glycol is initiation material by carbon dioxide, in the work of initiator and catalyst
With under, become to be obtained with epoxypropane copolymerization；The molecular weight of poly (propylene carbonate) glycol is 3000, poly (propylene carbonate) glycol
Hydroxy functionality is 2, and in poly (propylene carbonate) glycol molecules, the mole fraction of carbonate group is 30%.Diisocyanate is liquid
Change methyl diphenylene diisocyanate, chain extender is BDO, catalyst is stannous octoate, polymerization inhibitor is phosphoric acid, Halogen
Fire retardant is methyl-phosphoric acid dimethyl ester.
Embodiment 2
Weigh 100g poly (propylene carbonate) glycol, in the glass reaction kettle with vacuum extractor, 120 DEG C of evacuation take off
Water 2 hours, after dropping to room temperature, is mixed with 0.01g polymerization inhibitor, 70g diisocyanate and 0.02g catalyst, anti-in 80 DEG C of stirrings
After answering 3h, it is cooled to 40 DEG C, obtain the first product 1.
Weigh 10g fire retardant and 9.9g chain extender, in the glass reaction kettle with vacuum extractor, evacuation is dehydrated
Afterwards, after mixing with the first product 1,5min is reacted in vacuum outgass, obtains the second product 1.
Second product 1 is poured in preheated grinding tool immediately, is solidified after 12h with 80 DEG C in an oven, then in 100 DEG C of ripenings
12h, broken pelletize after room temperature standing 24h, obtain product 2.
In the present embodiment, poly (propylene carbonate) glycol is initiation material by carbon dioxide, in the work of initiator and catalyst
With under, become to be obtained with epoxypropane copolymerization；The molecular weight of poly (propylene carbonate) glycol is 3000, poly (propylene carbonate) glycol
Hydroxy functionality is 2, and in poly (propylene carbonate) glycol molecules, the mole fraction of carbonate group is 30%.Diisocyanate is liquid
Change methyl diphenylene diisocyanate, chain extender is BDO, catalyst is stannous octoate, polymerization inhibitor is phosphoric acid, Halogen
Fire retardant is methyl-phosphoric acid dimethyl ester.
Embodiment 3
Weigh 100g poly (propylene carbonate) glycol, in the glass reaction kettle with vacuum extractor, 120 DEG C of evacuation take off
Water 2 hours, after dropping to room temperature, is mixed with 0.01g polymerization inhibitor, 80g diisocyanate and 0.02g catalyst, anti-in 80 DEG C of stirrings
After answering 3h, it is cooled to 40 DEG C, obtain the first product 1.
Weigh 10g fire retardant and 10.5g chain extender, in the glass reaction kettle with vacuum extractor, evacuation is dehydrated
Afterwards, after mixing with the first product 1,5min is reacted in vacuum outgass, obtains the second product 1.
Second product 1 is poured in preheated grinding tool immediately, is solidified after 12h with 80 DEG C in an oven, then in 100 DEG C of ripenings
12h, broken pelletize after room temperature standing 24h, obtain product 3.
In the present embodiment, poly (propylene carbonate) glycol is initiation material by carbon dioxide, in the work of initiator and catalyst
With under, become to be obtained with epoxypropane copolymerization；The molecular weight of poly (propylene carbonate) glycol is 3000, poly (propylene carbonate) glycol
Hydroxy functionality is 2, and in poly (propylene carbonate) glycol molecules, the mole fraction of carbonate group is 30%.Diisocyanate is liquid
Change methyl diphenylene diisocyanate, chain extender is BDO, catalyst is stannous octoate, polymerization inhibitor is phosphoric acid, Halogen
Fire retardant is methyl-phosphoric acid dimethyl ester.
Embodiment 4
Weigh 100g poly (propylene carbonate) glycol, in the glass reaction kettle with vacuum extractor, 120 DEG C of evacuation take off
Water 2 hours, after dropping to room temperature, is mixed with 0.01g polymerization inhibitor, 60g diisocyanate and 0.02g catalyst, anti-in 80 DEG C of stirrings
After answering 3h, it is cooled to 40 DEG C, obtain the first product 1.
Weigh 10g fire retardant and 8.5g chain extender, in the glass reaction kettle with vacuum extractor, evacuation is dehydrated
Afterwards, after mixing with the first product 1,5min is reacted in vacuum outgass, obtains the second product 1.
Second product 1 is poured in preheated grinding tool immediately, is solidified after 12h with 80 DEG C in an oven, then in 100 DEG C of ripenings
12h, broken pelletize after room temperature standing 24h, obtain product 4.
In the present embodiment, poly (propylene carbonate) glycol is initiation material by carbon dioxide, in the work of initiator and catalyst
With under, become to be obtained with epoxypropane copolymerization；The molecular weight of poly (propylene carbonate) glycol is 3000, poly (propylene carbonate) glycol
Hydroxy functionality is 2, and in poly (propylene carbonate) glycol molecules, the mole fraction of carbonate group is 30%.Diisocyanate is liquid
Change methyl diphenylene diisocyanate, chain extender is BDO, catalyst is stannous octoate, polymerization inhibitor is phosphoric acid, Halogen
Fire retardant is that bisphenol-A is double (diphenyl phosphoester).
Embodiment 5
Weigh 100g poly (propylene carbonate) glycol, in the glass reaction kettle with vacuum extractor, 120 DEG C of evacuation take off
Water 2 hours, after dropping to room temperature, is mixed with 0.01g polymerization inhibitor, 60g diisocyanate and 0.02g catalyst, anti-in 80 DEG C of stirrings
After answering 3h, it is cooled to 40 DEG C, obtain the first product 1.
Weigh each 5g and 8.5g chain extender of two kinds of fire retardants, in the glass reaction kettle with vacuum extractor, evacuation
After dehydration, after mixing with the first product 1,5min is reacted in vacuum outgass, obtains the second product 1.
Second product 1 is poured in preheated grinding tool immediately, is solidified after 12h with 80 DEG C in an oven, then in 100 DEG C of ripenings
12h, broken pelletize after room temperature standing 24h, obtain product 5.
In the present embodiment, poly (propylene carbonate) glycol is initiation material by carbon dioxide, in the work of initiator and catalyst
With under, become to be obtained with epoxypropane copolymerization；The molecular weight of poly (propylene carbonate) glycol is 3000, poly (propylene carbonate) glycol
Hydroxy functionality is 2, and in poly (propylene carbonate) glycol molecules, the mole fraction of carbonate group is 30%.Diisocyanate is liquid
Change methyl diphenylene diisocyanate, chain extender is BDO, catalyst is stannous octoate, polymerization inhibitor is phosphoric acid, Halogen
Fire retardant is methyl-phosphoric acid dimethyl ester, bisphenol-A is double (diphenyl phosphoester).
Comparative example 1
Weigh 100g and take polyether Glycols (220), in the glass reaction kettle with vacuum extractor, 120 DEG C of evacuation
Dehydration 2 hours, after dropping to room temperature, is mixed with 0.01g polymerization inhibitor, 70g diisocyanate and 0.02g catalyst, stirs at 80 DEG C
After reaction 3h, it is cooled to 40 DEG C, obtains the first product 1.
Weigh 5g fire retardant and 9g chain extender, in the glass reaction kettle with vacuum extractor, after evacuation dehydration, with
After first product 1 mixing, 5min is reacted in vacuum outgass, obtains the second product 1.
Second product 1 is poured in preheated grinding tool immediately, is solidified after 12h with 80 DEG C in an oven, then in 100 DEG C of ripenings
12h, broken pelletize after room temperature standing 24h, obtain product 6.
In the present embodiment, dihydroxylic alcohols are polyether Glycols, and the molecular weight of polyether Glycols is 2000, and hydroxy functionality is 2,
Diisocyanate is liquefaction methyl diphenylene diisocyanate, and chain extender is BDO, and catalyst is stannous octoate, inhibition
Agent is phosphoric acid, and halogen-free flame retardants is methyl-phosphoric acid dimethyl ester.
Comparative example 2
Weigh 100g and take polyether Glycols (220), in the glass reaction kettle with vacuum extractor, 120 DEG C of evacuation
Dehydration 2 hours, after dropping to room temperature, is mixed with 0.01g polymerization inhibitor, 70g diisocyanate and 0.02g catalyst, stirs at 80 DEG C
After reaction 3h, it is cooled to 40 DEG C, obtains the first product 1.
Weigh 15g fire retardant and 9g chain extender, in the glass reaction kettle with vacuum extractor, after evacuation dehydration,
After mixing with the first product 1,5min is reacted in vacuum outgass, obtains the second product 1.
Second product 1 is poured in preheated grinding tool immediately, is solidified after 12h with 80 DEG C in an oven, then in 100 DEG C of ripenings
12h, broken pelletize after room temperature standing 24h, obtain product 7.
In the present embodiment, dihydroxylic alcohols are polyether Glycols, and the molecular weight of polyether Glycols is 2000, and hydroxy functionality is 2,
Diisocyanate is liquefaction methyl diphenylene diisocyanate, and chain extender is BDO, and catalyst is stannous octoate, inhibition
Agent is phosphoric acid, and halogen-free flame retardants is methyl-phosphoric acid dimethyl ester.
Embodiment 6
The present embodiment is the specific embodiment measuring product 1～product 7 fire resistance and mechanical property, the mechanics being measured
Performance includes：Tensile strength, elongation at break and hardness.
6.1 fire resistances measure
Vertical combustion experiment is by the test of fire-protection rating UL-94.
6.2 stretching strength determination
Tensile strength presses GB/T528-2009 test.
6.3 elongation at breaks measure
Elongation at break presses GB/T528-2009 test.
6.4 hardness measurement
Shao's A hardness presses GB/T6031-1998 test.
The result of above-mentioned experiment gained is arranged in table 1.
Table 1：Properties of product measurement result
As can be drawn from Table 1, compared with polyether-type product, the product that is obtained by the present invention, fire resistance is good, with
When also there is good mechanical property.
Can show that from technique scheme the technical scheme that the present invention provides has advantages below：
First, in the technical scheme that the present invention provides, the poly (propylene carbonate) glycol molecules that raw material is selected are contained within a large number
Carbonic acid ester bond and ehter bond, these keys make poly (propylene carbonate) glycol when preparing generating polyurethane, not only between its molecule,
And all easily form stronger intramolecular and intermolecular hydrogen bonding at it and carbamate between, there are soft and hard segments simultaneously mutually micro-
, so that poly (propylene carbonate) diol type polyurethane elastomer has intensity height, the characteristic of wearability, material stretching is strong for isolating construction
Degree is high, and properties are excellent, have wide market prospect.
Second, in the technical scheme that the present invention provides, polyurethane elastomer is heated temperature of initial decomposition compared to traditional
Polyurethane elastomer is relatively low, and the carbon dioxide that decomposes produce is capable of the oxygen concentration on diluted material surface, suppression material
Burn further, thus improving the fire resistance of material, compared with other fire proofings, the addition of fire retardant also significantly subtracts
Few, cost reduces.
3rd, in the technical scheme that the present invention provides, from efficient halogen-free phosphorus-containing fire retardant agent, its feature phosphorus content is high,
Excellent flame retardancy, in polyurethane, addition is few；Have fire-retardant and drop low viscous dual function.
4th, the poly (propylene carbonate) glycol that the present invention uses is to be obtained with carbon dioxide for raw material, and cost is than relatively low
Honest and clean, after industrialization, significance is respectively provided with to environmental conservation, energy-saving and emission-reduction.
In sum, the invention provides a kind of compositionss, the raw material of described compositionss includes：Poly (propylene carbonate) two
Alcohol, diisocyanate, chain extender, catalyst, polymerization inhibitor and halogen-free flame retardants.Present invention also offers a kind of above-mentioned composition
Preparation method, present invention also offers the product that a kind of above-mentioned composition or above-mentioned preparation method obtain is in fire proofing field
Application.In the technical scheme that the present invention provides, the addition of fire retardant is few, and one of the material of preparing being used is with carbon dioxide
It is obtained for raw material, cost is than less expensive；Meanwhile, without there being halogen, do not result in secondary pollution, meet today's society ring
Protect the requirement of sustainable development.Through experimental tests can obtain, the product that the technical scheme that the present invention provides is obtained, and fire resistance is good
Good, high mechanical strength, there is good weatherability, wearability and oil resistivity.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of compositionss are it is characterised in that the raw material of described compositionss includes：Poly (propylene carbonate) glycol, diisocyanate,
Chain extender, catalyst, polymerization inhibitor and halogen-free flame retardants.
2. compositionss according to claim 1 are it is characterised in that in terms of mass parts, the raw material of described compositionss includes：Poly-
100 parts of polypropylene carbonate esterdiol, 60～90 parts of diisocyanate, 8～12 parts of chain extender, 0.01～1 part of catalyst, polymerization inhibitor
0.1～1 part and 5～15 parts of halogen-free flame retardants.
3. compositionss according to claim 1 are it is characterised in that the preparation method of described poly (propylene carbonate) glycol is：
With carbon dioxide as initiation material, in the presence of initiator and catalyst, become to be obtained with epoxypropane copolymerization；
The molecular weight of described poly (propylene carbonate) glycol is 1000～8000, the hydroxy functionality of described poly (propylene carbonate) glycol
For 2～6, in described poly (propylene carbonate) glycol molecules, the mole fraction of carbonate group is 0.25～0.45.
4. compositionss according to claim 1 are it is characterised in that described diisocyanate is selected from：Toluene di-isocyanate(TDI),
One or more of methyl diphenylene diisocyanate and liquefaction methyl diphenylene diisocyanate.
5. compositionss according to claim 1 are it is characterised in that described chain extender is selected from：Ethylene glycol, BDO and
One or more of diglycol.
6. compositionss according to claim 1 are it is characterised in that described catalyst is selected from：Stannous octoate, isooctyl acid are sub-
One or more of stannum, dibutyl tin laurate.
7. compositionss according to claim 1 are it is characterised in that described halogen-free flame retardants is：Methyl-phosphoric acid dimethyl ester and/
Or bisphenol-A is double (diphenyl phosphoester)；
Described polymerization inhibitor is selected from：Methyl-phosphoric acid dimethyl ester and/or bisphenol-A are double (diphenyl phosphoester).
8. a kind of preparation method including the compositionss described in claim 1 to 8 any one is it is characterised in that described preparation
Method is：
Step one, by after poly (propylene carbonate) diol dehydratase, mix with polymerization inhibitor, diisocyanate and catalyst, cold after stirring
But, obtain the first product；
Step 2, by after the fire retardant after dehydration and chain extender and described first product, vacuum outgass are reacted, and obtain the second product；
Step 3, described second product are poured in grinding tool, sequentially pass through solidification, ripening, after standing, broken pelletize, obtain product.
9. preparation method according to claim 8 it is characterised in that described in step one stirring temperature be 60～80 DEG C,
The time of stirring described in step one is 2～3h, and described in step one, the temperature of cooling is 40～50 DEG C；
Described in step 2, the time of vacuum outgass reaction is 5～10min；
Described in step 3, the time of solidification is 12h, and the temperature of solidification is 100 DEG C described in step 3, ripening described in step 3 when
Between be 12h, curing temperature described in step 3 is 120 DEG C, and the time of standing described in step 3 is 24h, standing described in step 3
Temperature is room temperature.
10. the compositionss described in a kind of inclusion claim 1 to 7 any one or the system described in claim 8 to 9 any one
The product that Preparation Method obtains is in the application in fire proofing field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610967065.2A CN106478926A (en) | 2016-10-28 | 2016-10-28 | A kind of compositionss and preparation method thereof and the application in fire proofing field |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610967065.2A CN106478926A (en) | 2016-10-28 | 2016-10-28 | A kind of compositionss and preparation method thereof and the application in fire proofing field |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106478926A true CN106478926A (en) | 2017-03-08 |
Family
ID=58272156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610967065.2A Pending CN106478926A (en) | 2016-10-28 | 2016-10-28 | A kind of compositionss and preparation method thereof and the application in fire proofing field |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106478926A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893304A (en) * | 2017-04-05 | 2017-06-27 | 广东工业大学 | A kind of flame-retardant polyurethane elastomer and preparation method thereof |
| CN109400846A (en) * | 2018-10-27 | 2019-03-01 | 濮阳天健生物科技有限公司 | A kind of chemical reaction kettle composite insulation boards and preparation method thereof |
| CN117843678A (en) * | 2023-12-29 | 2024-04-09 | 珠海宏昌电子材料有限公司 | Diisocyanate monomer and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838717A (en) * | 2011-10-25 | 2012-12-26 | 海南大学 | Preparation of thermoplastic polyurethane elastomer with polypropylene carbonate as soft segment |
| US20140378624A1 (en) * | 2010-12-28 | 2014-12-25 | Sk Innovation Co., Ltd. | Method for Improving Thermal Stability of Polypropylene Carbonate |
| CN105254838A (en) * | 2015-11-16 | 2016-01-20 | 济南泰星精细化工有限公司 | Body halogen-free flame retardant TPU modified material and preparing method thereof |
-
2016
- 2016-10-28 CN CN201610967065.2A patent/CN106478926A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140378624A1 (en) * | 2010-12-28 | 2014-12-25 | Sk Innovation Co., Ltd. | Method for Improving Thermal Stability of Polypropylene Carbonate |
| CN102838717A (en) * | 2011-10-25 | 2012-12-26 | 海南大学 | Preparation of thermoplastic polyurethane elastomer with polypropylene carbonate as soft segment |
| CN105254838A (en) * | 2015-11-16 | 2016-01-20 | 济南泰星精细化工有限公司 | Body halogen-free flame retardant TPU modified material and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐守萍等: ""聚碳酸亚乙酯聚氨酯弹性体的合成与性能"", 《聚氨酯工业》 * |
| 陈伟彬等: ""聚碳酸亚丙酯聚氨酯弹性体的合成与性能"", 《高分子材料科学与工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893304A (en) * | 2017-04-05 | 2017-06-27 | 广东工业大学 | A kind of flame-retardant polyurethane elastomer and preparation method thereof |
| CN109400846A (en) * | 2018-10-27 | 2019-03-01 | 濮阳天健生物科技有限公司 | A kind of chemical reaction kettle composite insulation boards and preparation method thereof |
| CN117843678A (en) * | 2023-12-29 | 2024-04-09 | 珠海宏昌电子材料有限公司 | Diisocyanate monomer and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448202B (en) | Phosphor-containing flame-proof method for preparing thermoplastic polyurethane elastomer | |
| ES2352334T3 (en) | THERMOPLASTIC POLYURETHANE FLAME RETARDER WITHOUT HALOGEN. | |
| US20220033694A1 (en) | Soft solvent-free flame-retardant polyurethane synthetic leather and preparation method therefor | |
| CN106478926A (en) | A kind of compositionss and preparation method thereof and the application in fire proofing field | |
| CN111849410A (en) | Halogen-free flame-retardant heat-conducting polyurethane pouring sealant and preparation method thereof | |
| CN102010494B (en) | Light-cured resin with low water absorption and preparation method thereof | |
| CN102964562B (en) | Polyurethane elastomer composite material for paving warship ground and preparation method thereof | |
| CN103665829B (en) | Environment protection high flame resistance method for preparing thermoplastic polyurethane elastomer | |
| Wang et al. | Synthesis of reactive DOPO-based flame retardant and its application in polyurethane elastomers | |
| CN104046224B (en) | A kind of preparation method of aqueous flame retardant polyurethane coating | |
| CN105367767A (en) | Saturated middle hydroxyl value polyester resin for high flexibility powder coating and preparation method thereof | |
| CN115850641B (en) | Flame-retardant modified polyurethane material and synthesis method thereof | |
| CN106674467A (en) | Environment-friendly polyurethane prepolymer and preparation method thereof | |
| CN114573775B (en) | Phosphorus-containing flame-retardant copolymerized aqueous polyurethane and preparation method thereof | |
| CN103910844B (en) | A kind of halogen-free low-smoke rigid polyurethane foam and preparation method thereof | |
| CN104540924A (en) | Halogen-free flame retardant TPU with very high LOI | |
| CN112375527A (en) | Foaming polyurethane sealant composite material for battery and preparation method thereof | |
| CN112250828A (en) | High-insulation low-temperature-expansion-resistant flame-retardant polyurethane material and preparation method and application thereof | |
| CN110746923B (en) | Flame-retardant heat-resistant double-component polyurethane lawn gum for artificial lawn | |
| CN106432676A (en) | Preparation method of N/P/nano synergistic flame-retardant waterborne polyurethane dispersion liquid | |
| CN106893304A (en) | A kind of flame-retardant polyurethane elastomer and preparation method thereof | |
| KR20160038170A (en) | Method for preparing of environment-friendly flame retardancy polyurethane resin including phosphorus | |
| CN102977310A (en) | Flame-resistant spray coating polyurethane rigid foam material | |
| CN115386065B (en) | Preparation method of synergistic flame-retardant polyurethane elastomer | |
| CN101508939A (en) | Structure type flame-proof ricinus oil based polylol and uses in polyurethane foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170308 |
|
| RJ01 | Rejection of invention patent application after publication |