CN108102271A - Preparation method and the application of a kind of flame-proof acrylic ester plastics and its casting plate - Google Patents
Preparation method and the application of a kind of flame-proof acrylic ester plastics and its casting plate Download PDFInfo
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- CN108102271A CN108102271A CN201711156089.0A CN201711156089A CN108102271A CN 108102271 A CN108102271 A CN 108102271A CN 201711156089 A CN201711156089 A CN 201711156089A CN 108102271 A CN108102271 A CN 108102271A
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- plastics
- flame
- alkyl
- fire retardant
- retardant
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
Abstract
The invention discloses the preparation method and application of a kind of polypropylene flame redardant acids plastics and its casting plate.Fire retardant disclosed by the invention includes ionic liquid component, and wherein ionic liquid can be shared with single ionic liquid components or several ionic liquids or ionic liquid is mixed with conventional flame retardant.Polyacrylic plastics parent and the plastic extrusion plate of the extruded machine blending of fire retardant.After fire retardant can also be mixed with acrylic monomer, then it polymerize, obtains flame-proof acrylic ester plastic pouring plate.Flame-proof acrylic ester plastic plate disclosed by the invention can be used for illuminating, automobile, building, the fields such as advertisement.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of preparation method of acrylic board.
Background technology
It is referred to as acrylics, corresponding plastics system by the obtained polymer of polymerizable raw material of acrylicacidandesters class
Claim polyacrylic plastics, wherein most widely used with polymethyl ester methyl ester.Polymethyl methacrylate abbreviation code name be
PMMA is commonly called as organic glass.This macromolecule transparent material is the high-molecular compound formed by methyl methacrylate polymerization.It is
It is a kind of to develop important thermoplastic earlier.Organic glass be widely used in building, advertisement, traffic, medicine, civil goods, with
And commercial Application：Instrument surface plate and protecting cover etc. and illumination application：Fluorescent lamp, pendent lamp, street lamp cover etc..
Polymethyl methacrylate is easy to burn, and has limited oxygen index only 17.3, is much needing the fire-retardant place can not
It uses, this point is very unfortunate.However the fire-retardant of PMMA is not easy to, because PMMA is mostly used for transparent field, should keep
Bright property, reaches fire protection requirement again, and such fire retardant is seldom！Domestic and international available fire retardant probably has：
Sandoflame5060, brominated phosphate CBP, dimethyl methyl phosphonate DMMP, diethylhexyl tetrabromo-phthalate
TBPH etc., nevertheless, to reach UL94V0 ranks also extremely difficult for these fire retardants, additive amount often to reach 30% with
Upper even 40%, this is why few on the market see fire-retardant transparent PMMA materials.
The content of the invention
Goal of the invention：In order to solve the deficiencies in the prior art, the present invention provides a kind of preparation method of acrylic board,
In, the fire retardant in the present invention can be used for the preparation of PMMA extrusion boards.This based flame retardant can be used for extrusion board or cast
Plate can be addition type or reactive.
Technical solution：A kind of polypropylene flame redardant acids plastics, the fire retardant include ionic liquid ingredient, and molecular formula is such as
Under：A+B-；The structure of cation can be one kind in having structure：
Wherein, R (0-5) can choose from following groups respectively：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C
(3-10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base
(Cl-C8) alkyl；
Above-mentioned group can not have substituent group, it is possibility to have substituents group：One or two halogen, nitro, three fluoro
Methyl, trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O)
(OC(1-5))2；
It is chosen in the anion that anion can be listed from having structure：
Wherein, R chooses from following groups：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-10) cycloalkanes
Base, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base (Cl-C8) alkane
Base.Above-mentioned group can not have substituent group, it is possibility to have substituents group：One or two halogen, nitro, trifluoromethy,
Trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC (1-
5))2。
As an optimization：The fire retardant can be single ionic liquid or several ionic liquids are used with,
But it is mixed with conventional flame retardant, including：Inorganic combustion inhibitor, halogenated flame retardant, phosphorus and phosphine flame retardant, nitrogenated flame retardant.
As an optimization：The polyacrylic plastics refers to polymethyl methacrylate (PMMA) and its copolymer, including
Methyl methacrylate and styrol copolymer, methyl methacrylate, styrene, nitrile rubber copolymer, methacrylic acid
Copolymer, the poly- α-chloro-acrylicacid of methyl esters and styrene, butadiene rubber copolymer, methyl methacrylate and methyl acrylate
Methyl esters, poly- Mecrilate.
As an optimization：The additive amount of the fire retardant accounts for the 0.1%-50% of the ratio of entire monomer or is 1%-
40% is either 3%-30% or is 5%-20%.
A kind of preparation method of the casting plate of polypropylene flame redardant acids plastics, the flame retardant plastics can be by squeezing out poly- third
Olefin(e) acid class plastics parent and fire retardant obtain plastic extrusion plate, after fire retardant can also be mixed with acrylic monomer, then polymerize, obtain
The casting plate of flame-proof acrylic ester plastics.
A kind of application of polypropylene flame redardant acids plastics described in basis, the polypropylene flame redardant acids plastics are used to build
Build, advertisement, traffic, medicine, civil goods, commercial Application and illumination application, described industrially applies to：Instrument surface plate and shield
Lid, the illumination are applied to：Fluorescent lamp, pendent lamp, street lamp cover.
Advantageous effect：The specific advantage of the present invention is as follows：
(1) the ionic liquid fire retardant in the present invention will not volatilize, and also predominantly stay in solid phase in burning and play resistance
Combustion acts on.And traditional phosphate belongs to semi-volatile compounds, when burning, can evaporate into gas phase.Phosphoric acid is disclosed in spite of research
Ester also may have fire retardation, but effect unobvious in gas phase.Therefore, ionic liquid fire retardant is than traditional phosphate flame retardant
Flame retardant effect is more excellent.
(2) " designability " of the structure of the ionic liquid in the present invention, can provide optimal phase for different plastic products
The fire retardant design of capacitive.Splendid compatibility causes fire retardant to uniformly disperse or even be dissolved in plastics, so as to plastics
The influence of physical mechanical property is minimum.The transparency of transparent plastic can be unaffected.
(3) different points are introduced between fire retardant and plastics macromolecular chain due to the special structure of " ion " in the present invention
Sub- power, so as to reduce fire retardant plasticising side effect so that the glass transition temperature of plastics either heat distortion temperature do not decline or
Decline few.
(4) present invention in more than the melt temperature of plastics, the molecular separating force between fire retardant and plastics macromolecule is beaten
Broken, fire retardant plays the role of processing aid again, effectively reduces the viscosity of the melt of plastics, and can reduce plastic processing temperature and
The molding defect rate of plastic product.
(5) there is good dissolubility to organic matter, inorganic matter, high molecular material due to ionic liquid in the present invention,
Ionic liquid fire retardant can be with conventional flame retardant compounding use, and can improve the compatibility of conventional flame retardant in the plastic and disperse
Property, reduce the influence to plastics physical mechanical property.
(6) the ionic liquid fire retardant in the present invention can be used for the preparation of PMMA extrusion boards or casting plate using simply,
It can be used for being surface-treated.
Description of the drawings
Fig. 1 is the cationic structural schematic diagram in the fire retardant in the present invention；
Fig. 2 is the anion structure schematic diagram in the fire retardant in the present invention.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, so that the technology of this field
Personnel can be better understood from advantages and features of the invention, so as to make apparent boundary to protection scope of the present invention
It is fixed.Embodiment described in the invention is only part of the embodiment of the present invention, instead of all the embodiments, based on the present invention
In embodiment, the every other implementation that those of ordinary skill in the art are obtained on the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
As shown in Figs. 1-2, a kind of polypropylene flame redardant acids plastics, the fire retardant include ionic liquid ingredient, molecule
Formula is as follows：A+B-；The structure of cation can be one kind in having structure：
Wherein, R (0-5) can choose from following groups respectively：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C
(3-10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base
(Cl-C8) alkyl；
Above-mentioned group can not have substituent group, it is possibility to have substituents group：One or two halogen, nitro, three fluoro
Methyl, trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O)
(OC(1-5))2；
It is chosen in the anion that anion can be listed from Fig. 2, wherein, R chooses from following groups：Hydrogen, C (1-20) alkane
Base, aromatic radical, C (3-10) heterocycle, C (3-10) cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkane
Base, heterocyclic aromatic base and heterocyclic aromatic base (Cl-C8) alkyl.Above-mentioned group can not have substituent group, it is possibility to have substituents
Group：One or two halogen, nitro, trifluoromethy, trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-
NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC (1-5)) 2.
The fire retardant can be single ionic liquid or several ionic liquids are used with or and passed
System fire retardant is used with, including：Inorganic combustion inhibitor, halogenated flame retardant, phosphorus and phosphine flame retardant, nitrogenated flame retardant.
The polyacrylic plastics refers to polymethyl methacrylate (PMMA) and its copolymer, including methacrylic acid
Methyl esters and styrol copolymer, methyl methacrylate, styrene, nitrile rubber copolymer, methyl methacrylate and benzene second
Alkene, butadiene rubber copolymer, the copolymer of methyl methacrylate and methyl acrylate, poly- methyl α-chloroacrylate, poly- α-
Methyl 2-cyanoacrylate.
The additive amount of the fire retardant account for the 0.1%-50% of the ratio of entire monomer either for 1%-40% or
For 3%-30% or it is 5%-20%.
The preparation method of the casting plate of the polypropylene flame redardant acids plastics, the flame retardant plastics can be poly- by squeezing out
Acrylics parent and fire retardant obtain plastic extrusion plate, after fire retardant can also be mixed with acrylic monomer, then polymerize,
Obtain the casting plate of flame-proof acrylic ester plastics.
The application of the polypropylene flame redardant acids plastics, the polypropylene flame redardant acids plastics for build, advertisement,
Traffic, medicine, civil goods, commercial Application and illumination application, described industrially applies to：Instrument surface plate and protecting cover, it is described
Illumination is applied to：Fluorescent lamp, pendent lamp, street lamp cover.
Case study on implementation 1.
1- amyl -3- methyl miaow Cuo bromides
By 20% 1- amyl -3- methyl miaow Cuo bromides compounds and acryl resin particle extruder melt blending.
Liquor charger is also equipped on extruder, extrusion temperature is slightly below the processing temperature of pure acryl resin.Then it is molded mechanism
Standby batten, tests flame retardant property.
Case study on implementation 2.
N- butyl-N- methyl piperidine bromides
The processing test technology of case study on implementation 2 above is all similar with case 1, no longer repeats.Wherein, compound is N- fourths
Base-N- methyl piperidine bromide compounds.
Fire retardant in the present invention is based on ion liquid compound.Ionic liquid refers in room temperature or close to being at room temperature
Salt showing liquid, being made of completely zwitterion, also referred to as low temperature molten salt.Ionic liquid as ionic compound,
Lower melting-point main cause is because the asymmetry of some substituent groups in its structure prevents ion from being regularly piled into crystal
It is caused.
It is made of organic cation and inorganic or organic anion, it is described cation See Figure 1, have quaternary ammonium salt from
Son, quaternary phosphine salt ion, imidazolium ion and pyrroles's salt ion etc..The anion See Figure 2, there is halide ion, tetrafluoro boric acid
Radical ion, hexafluorophosphoricacid acid ions, phosphate anion, sulphonic acid ester anion etc..
The flame retardant property of the sample of the acrylic board prepared in the present invention is all significantly improved：The longer time is needed just may be used
Sample to be lighted；Sample in air can self-extinguishment；Smoke density when resin burns is substantially reduced.Ionic liquid in the present invention
Fire retardant can be used for the preparation of casting plate.
Ionic liquid fire retardant in the present invention will not volatilize, and also predominantly stay in solid phase in burning and play fire-retardant work
With.And traditional phosphate belongs to semi-volatile compounds, when burning, can evaporate into gas phase.Disclosing phosphate in spite of research can
Also can there are fire retardation, but effect unobvious in gas phase.Therefore, ionic liquid fire retardant is more fire-retardant than traditional phosphate flame retardant
Effect is more excellent.
" designability " of the structure of ionic liquid in the present invention can provide optimal compatibility for different plastic products
Fire retardant design.Splendid compatibility causes fire retardant to uniformly disperse or even be dissolved in plastics, so as to the physics to plastics
The influence of mechanical performance is minimum.The transparency of transparent plastic can be unaffected.
Different molecules is introduced between fire retardant and plastics macromolecular chain due to the special structure of " ion " in the present invention
Power, so as to reduce fire retardant plasticising side effect so that the glass transition temperature of plastics either heat distortion temperature do not decline or under
Drop is few.
In the present invention more than the melt temperature of plastics, the molecular separating force between fire retardant and plastics macromolecule is broken,
Fire retardant plays the role of processing aid again, effectively reduces the viscosity of the melt of plastics, and can reduce temperature and the modeling of plastic processing
Expect the defect rate of formed product.
There are good dissolubility, ion to organic matter, inorganic matter, high molecular material due to ionic liquid in the present invention
Liquid flame retardant can be with conventional flame retardant compounding use, and can improve the compatibility and dispersiveness of conventional flame retardant in the plastic,
Reduce the influence to plastics physical mechanical property.
Ionic liquid fire retardant in the present invention can be used for the preparation of PMMA extrusion boards or casting plate using simply,
It can be used for being surface-treated.
Claims (6)
1. a kind of polypropylene flame redardant acids plastics, it is characterised in that：The fire retardant includes ionic liquid ingredient, and molecular formula is such as
Under：A+B-；The structure of cation can be one kind in having structure：
Wherein, R (0-5) can choose from following groups respectively：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-10)
Cycloalkyl, (C3-ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base (Cl-
C8) alkyl；
Above-mentioned group can not have substituent group, it is possibility to have substituents group：One or two halogen, nitro, trifluoromethy,
Trifluoromethoxy, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC (1-
5))2；
It is chosen in the anion that anion can be listed from having structure：
Wherein, R chooses from following groups：Hydrogen, C (1-20) alkyl, aromatic radical, C (3-10) heterocycle, C (3-10) cycloalkyl, (C3-
ClO) heterocycle (C1-C8) alkyl, aromatic radical (Cl-C8) alkyl, heterocyclic aromatic base and heterocyclic aromatic base (Cl-C8) alkyl.It is above-mentioned
Group can not have substituent group, it is possibility to have substituents group：One or two halogen, nitro, trifluoromethy, three fluoro first
Oxygroup, methoxyl group, carboxyl ,-NH2 ,-OH ,-SH ,-NHCH3 ,-N (CH3) 2, cyano ,-SO3H ,-P (O) (OC (1-5)) 2.
2. polypropylene flame redardant acids plastics according to claim 1, it is characterised in that：The fire retardant can be single
Ionic liquid or several ionic liquids use with or mixed with conventional flame retardant, including：Inorganic combustion inhibitor, halogen
Flame retardant, phosphorus and phosphine flame retardant, nitrogenated flame retardant.
3. polypropylene flame redardant acids plastics according to claim 1, it is characterised in that：The polyacrylic plastics refers to
Polymethyl methacrylate (PMMA) and its copolymer, including methyl methacrylate and styrol copolymer, methacrylic acid
Methyl esters, styrene, nitrile rubber copolymer, methyl methacrylate and styrene, butadiene rubber copolymer, methyl methacrylate
The copolymer of ester and methyl acrylate, poly- methyl α-chloroacrylate, poly- Mecrilate.
4. polypropylene flame redardant acids plastics according to claim 1, it is characterised in that：The additive amount of the fire retardant accounts for
The 0.1%-50% of the ratio of entire monomer is either that 1%-40% is either 3%-30% or is 5%-20%.
5. a kind of preparation method of the casting plate of polypropylene flame redardant acids plastics according to claim 1, it is characterised in that：
The flame retardant plastics can be by squeezing out polyacrylic plastics parent and fire retardant obtains plastic extrusion plate, and fire retardant can also be with
After acrylic monomer mixing, then it polymerize, obtains the casting plate of flame-proof acrylic ester plastics.
6. a kind of application of polypropylene flame redardant acids plastics according to claim 1, it is characterised in that：Described is fire-retardant poly-
Acrylics for build, advertisement, traffic, medicine, civil goods, commercial Application and illumination application, the commercial Application
In：Instrument surface plate and protecting cover, the illumination are applied to：Fluorescent lamp, pendent lamp, street lamp cover.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711156089.0A CN108102271A (en) | 2017-11-20 | 2017-11-20 | Preparation method and the application of a kind of flame-proof acrylic ester plastics and its casting plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711156089.0A CN108102271A (en) | 2017-11-20 | 2017-11-20 | Preparation method and the application of a kind of flame-proof acrylic ester plastics and its casting plate |
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| Publication Number | Publication Date |
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|---|---|---|---|
| CN201711156089.0A Pending CN108102271A (en) | 2017-11-20 | 2017-11-20 | Preparation method and the application of a kind of flame-proof acrylic ester plastics and its casting plate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909503A (en) * | 2019-05-07 | 2020-11-10 | 南通诺为新材料科技有限公司 | Flame-retardant thermoplastic polyurethane plastic, flame retardant and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633702A (en) * | 2016-12-28 | 2017-05-10 | 宁波优科泰科技发展有限公司 | Flame-retardant plastic using ionic liquid as flame retardant and preparation method thereof |
-
2017
- 2017-11-20 CN CN201711156089.0A patent/CN108102271A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633702A (en) * | 2016-12-28 | 2017-05-10 | 宁波优科泰科技发展有限公司 | Flame-retardant plastic using ionic liquid as flame retardant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王文广主编: "《塑料配方设计》", 30 September 1998, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909503A (en) * | 2019-05-07 | 2020-11-10 | 南通诺为新材料科技有限公司 | Flame-retardant thermoplastic polyurethane plastic, flame retardant and application |
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Application publication date: 20180601 |