CN103122105B - Fire-retarding PS (Poly Styrene) as well as preparation method and product thereof - Google Patents
Fire-retarding PS (Poly Styrene) as well as preparation method and product thereof Download PDFInfo
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- CN103122105B CN103122105B CN201310043581.2A CN201310043581A CN103122105B CN 103122105 B CN103122105 B CN 103122105B CN 201310043581 A CN201310043581 A CN 201310043581A CN 103122105 B CN103122105 B CN 103122105B
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Abstract
The invention discloses a fire-retarding PS as well as a preparation method and a product thereof. The fire-retarding PS comprises the following components in parts by weight: 100 parts of PS resin, 5-64 parts of a fire retardant, 1-60 parts of a flame retardant synergist, 0-50 parts of an additive, 0-100 parts of filler and 1-10 parts of other additives, wherein the sum of the weight parts of the fire retardant and the flame retardant synergist is 25-65; the flame retardant synergist is ammonium salt at least containing one NH4<+1>; and other additives are carbon forming agents and/or stabilizing agents. By reasonably selecting the flame retardant synergist, the fire-retarding PS disclosed by the invention can greatly improve the fire retarding efficiency of hypophosphite or alkyl phosphinic salt fire retardant in PS resin and greatly reduces use of the hypophosphite or alkyl phosphinic salt fire retardant in PS resin, so that PS reaches a high fire retardant rating at a low additive amount condition of the fire retardant.
Description
Technical field
The present invention relates to flame retardance of polymer field, particularly fire-retardant PS of one and preparation method thereof and goods.
Background technology
In existing flame-retardant modified PS, in order to meet non-halogen requirement, need to prepare alloy with PPE more, then select phosphorous, nitrogen or its compound system.The phosphonium flame retardant that present use is the most general and composition thereof mainly contain microencapsulated powder oil, phosphoric acid ester, Intumscent Flame Retardant System etc. based on ammonium polyphosphate.These flame-retardant systems are all realize fire-retardant by solid phase mechanism.Compare with the bromo-antimony compounding flame retardant of tradition, the phosphonium flame retardant of solid phase fire retardant mechanism and compounding flame retardant thereof, have the shortcoming that flame retarding efficiency is low.
Phosphinates is the phosphonium flame retardant that a class can act on gas phase, but there is the low problem of flame retarding efficiency equally, and not during compositional flame-retardant synergist, need adding a large amount of phosphinates, just can to reach UL94V-0 level fire-retardant.Patent CN1660857B and CN100348653C discloses the composition of a kind of alkyl phosphinate composite amino-contained ring texture fire retarding synergist, although these fire retarding synergists can play synergistic effect to a certain extent, but its synergistic limitation, and therefore the consumption of phosphinates is still higher, greatly increase the cost of fire-retardant combination.
Summary of the invention
Goal of the invention of the present invention is to overcome the deficiencies in the prior art, provides a kind of fire-retardant PS, and this fire-retardant PS, by the choose reasonable to fire retarding synergist, when fire retardant addition is less, can reach high flame retardant rating.
Another object of the present invention, is the preparation method providing described fire-retardant PS.
Another object of the present invention, is the goods providing described fire-retardant PS to prepare.
Above-mentioned purpose of the present invention, is achieved by following technical solution:
A kind of fire-retardant PS, in described fire-retardant PS, comprises the component calculated by weight as follows:
PS resin 100 parts;
Fire retardant 5 ~ 64 parts;
Fire retarding synergist 1 ~ 60 part;
Additive 0 ~ 50 part;
Filler 0 ~ 100 part;
Other auxiliary agent 0 ~ 10 part;
Wherein, the weight part sum of described fire retardant and fire retarding synergist is 25 ~ 65 parts;
Described fire retardant has structure shown in formula I:
Wherein, R
1and R
2can simultaneously or be asynchronously hydrogen or alkyl, M be Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or be protonated nitrogen base, and wherein m is 1,2,3 or 4;
Described fire retarding synergist is at least containing a NH
4 +ammonium salt;
Described additive is char-forming agent and/or stablizer.
A kind of fire-retardant PS, in described fire-retardant PS, is made up of the component calculated by weight as follows:
PS resin 100 parts;
Fire retardant 5 ~ 64 parts;
Fire retarding synergist 1 ~ 60 part;
Additive 0 ~ 50 part;
Filler 0 ~ 100 part;
Other auxiliary agent 0 ~ 10 part;
Wherein, the weight part sum of described fire retardant and fire retarding synergist is 25 ~ 65 parts;
Described fire retardant has structure shown in formula I:
Wherein, R
1and R
2can simultaneously or be asynchronously hydrogen or alkyl, M be Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or be protonated nitrogen base, and wherein m is 1,2,3 or 4;
Described fire retarding synergist is at least containing a NH
4 +ammonium salt;
Described additive is char-forming agent and/or stablizer.
Wherein, described PS resin is the vinyl aromatic monomers polymkeric substance of the PS resin of the modified rubber that this area is commonly used, the graft rubber polymer containing 5wt%-15wt% and 85wt%-95wt%.
Wherein, described filler is the filler that this area is commonly used, it acts on the effect normally played enhancing to the performance of PS, improve dimensional stability or meet some special purposes, and these fillers can be glass fibre, carbon fiber, natural fiber, talcum powder, kaolin, wollastonite, mica, wilkinite, glass microballon, calcium carbonate, barium sulfate etc.
Wherein, described char-forming agent is the char-forming agent that this area is commonly used, its effect helps matrix resin to form stable, firm layer of charcoal in combustion, thus reaching the fire retardation of oxygen barrier every matter, described char-forming agent is selected from the mixture of tetramethylolmethane, pentaerythritol ester, novolac, Mierocrystalline cellulose etc. or these materials.
Wherein, described stablizer is the stablizer that this area is commonly used, its effect is the stability of composite flame-retardant agent in processing and moulding process improving time phosphine (phosphorus) hydrochlorate fire retardant and fire retarding synergist composition thereof, and described stablizer is selected from the mixture of magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, stannic oxide, zinc borate, zinc, zinc hydroxyl stannate etc. or these materials.
Wherein, the weight part that described fire retardant adds is 5 ~ 44 parts; More preferably the weight part added is 5 ~ 25 parts.
Wherein, the weight part that described fire retarding synergist adds is 1 ~ 40 part; More preferably the weight part added is 20 ~ 40 parts.
Wherein, described additive weight part is 0 ~ 25 part.
Wherein, the weight part 0 ~ 80 part of described glass fibre interpolation.
Wherein, the weight part 0 ~ 5 part of described other auxiliary agents interpolation.
Wherein, the weight part of described fire retardant is 5 ~ 25 parts; The weight part of fire retarding synergist is 20 ~ 40 parts.
Wherein, the weight part sum of described fire retardant and fire retarding synergist is preferably 33 ~ 45 parts.
Wherein, the heat decomposition temperature of described fire retarding synergist is more than 180 DEG C.
Wherein, the negative ion of described fire retarding synergist is SO
4 2-, HSO
4 -,s
2o
7 2-, Br
-, Cl
-, the aliphatic carboxylic acid root of C1 ~ C3 or the aromatic carboxylic acid root of C7 ~ C10.
Wherein, described fire retarding synergist is ammonium sulfate, aluminium ammonium sulfate, ammonium sulfate magnesium, ammonium sulfate zinc, ammonium sulfate calcium, ammonium sulfate iron, monoammonium sulfate, ammonium pyrosulfate, ammonium chloride, brometo de amonio, ammonium formiate, ammonium acetate, propionic acid ammonium, isopropyl acid ammonium, ammonium benzoate, toluylic acid ammonium, ammonium phthalate, m-phthalic acid ammonium, terephthalic acid ammonium, phenylpropionic acid ammonium, 2-methylphenyl acetic acid ammonium, 3-methylphenyl acetic acid ammonium, 4-methylphenyl acetic acid ammonium, 2-ethyl benzoate ammonium, 3-ethyl benzoate ammonium, 4-ethyl benzoate ammonium.
Wherein, described fire retarding synergist is ammonium sulfate, aluminium ammonium sulfate, monoammonium sulfate, ammonium pyrosulfate, ammonium chloride or brometo de amonio.
Wherein, in described fire retardant, R
1and R
2it can simultaneously or be asynchronously the alkyl of hydrogen or C1 ~ C6.
Wherein, in described fire retardant, M is Al, Mg, Ca, Zn, Sn or Fe.
Wherein, described fire retardant is hypo-aluminum orthophosphate, magnesium hypophosphite, calcium propionate, ferric hypophosphite, aluminum diethylphosphinate, diethyl phospho acid magnesium, diethyl phospho acid zinc, diethyl phospho acid calcium, diethyl phospho acid iron, dimethylphosphinic acid aluminium, dimethylphosphinic acid magnesium, dimethylphosphinic acid zinc, dimethylphosphinic acid calcium, dimethylphosphinic acid iron, dipropyl phospho acid aluminium, dibutyl phospho acid aluminium, diamyl phospho acid aluminium, dihexyl phospho acid aluminium, methylethyl phospho acid aluminium, methylpropylphosphinic acid aluminium, methyl butyl phospho acid aluminium, ethyl propyl phospho acid aluminium, ethyl-butyl phospho acid aluminium, monomethyl phospho acid aluminium, single ethylphosphinic acid aluminium, single propylphosphinic acid aluminium, monobutyl phospho acid aluminium, single amyl group phospho acid aluminium, single ethylhexyl hypophosphorous acid aluminium, monomethyl phospho acid magnesium, single ethylphosphinic acid magnesium, single propylphosphinic acid magnesium, monobutyl phospho acid magnesium, monomethyl phospho acid calcium, single ethylphosphinic acid calcium, single propylphosphinic acid calcium, monobutyl phospho acid calcium.
The preparation method of described fire-retardant PS, is characterized in that, comprises the steps: said components to be mixed in proportion, extrudes and obtain at 180 ~ 230 DEG C.
The goods be made up of described fire-retardant PS.
Compared with prior art, the present invention has following beneficial effect:
The present invention is by the choose reasonable to fire retarding synergist, significantly can improve hypophosphite or the flame retarding efficiency of alkyl phosphinate fire retardant in PS resin, greatly reduce the consumption of hypophosphite or alkyl phosphinate fire retardant in PS resin, therefore when fire retardant addition is less, the flame retardant rating that PS reaches high can be made.
Embodiment
Below in conjunction with some embodiments, composite flame-retardant agent of the present invention, preparation method and application thereof are described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Embodiments of the invention adopt following raw material:
Hypophosphite used in embodiment, purchased from continent, Wuhan chemical industry;
Dialkylphosphinic salts, purchased from German Clariant;
Ammonium sulfate, purchased from Baoqing, Yueyang Chemical Co., Ltd.;
Ammonium chloride, purchased from Zhuzhou Jianghai Environmental Protection Co., Ltd.;
Brometo de amonio, reaches chemical industry purchased from Suzhou City;
Ammonium pyrosulfate, purchased from Beijing Heng Yezhongyuan Chemical Co., Ltd.;
Aluminium ammonium sulfate, purchased from Wuhan Jin Nuo Chemical Co., Ltd.;
Ammonium formiate, purchased from Shanghai Jin Cheng Chemical Co., Ltd.;
Ammonium benzoate, purchased from Shanghai Jin Cheng Chemical Co., Ltd.;
Novolac: PF-204, Yong Hui Chemical Co., Ltd. of Huantai County;
Zinc oxide: rubber grade zinc oxide, Weifang Long Daxin industry company limited;
PS-1:PS 1300, graft rubber polymer content is 6 ~ 8%, DOW Chemical;
PS-2:PS 1110, graft rubber polymer content is 8 ~ 10%, DOW Chemical;
Filler: glass fibre, megalith company.
Composition vertical combustion grade criterion: UL-94;
Extrude processing characteristics criterion: by visual inspection extruding pelletization process, whether the material strip extruded has the situation such as foaming, variable color, surface irregularity to occur, according to extruding material strip foaming, variable color, surface roughness judgement extrude processing characteristics.When the situations such as foaming, variable color, surface irregularity do not appear in material strip, extrude processing characteristics as well; When the situations such as few foaming, light discolouration, surface not roughen appear in material strip, extrude processing characteristics and decompose for slight; Material strip occur less foaming, light discolouration, surface slightly the situation such as roughen but still can accept time, extruding processing characteristics is decomposed.
Be illustrated in the mode of specific embodiment below, described raw material is weight part.
Embodiment 1 ~ 18 and comparative example 1 ~ 6
In the ratio that table 1 ~ 3 are recorded, each component is mixed, extrudes at 180 ~ 230 DEG C, prepare the fire-retardant PS of embodiment 1 ~ 18 and comparative example 1 ~ 6.The test result of its flame retardant properties and processing characteristics is as shown in table 4.
Table 1
Table 2
Table 3
The performance test of embodiment 1 ~ 18 and comparative example 1 ~ 4 is as shown in table 4:
Table 4
From the results shown in Table 4, when the existing MCA/MPP of employing is not good as the flame retardant effect of fire retarding synergist.As can be seen from Table 4, fire-retardant PS of the present invention, by the choose reasonable to fire retardant and fire retarding synergist, when fire retardant addition is few, can reach high flame retardant effect.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (7)
1. a fire-retardant PS, is characterized in that, in described fire-retardant PS, is made up of the component calculated by weight as follows:
Wherein, the weight part sum of described fire retardant and fire retarding synergist is 25 ~ 65 parts;
Described fire retardant has structure shown in formula I:
Wherein, R
1and R
2can simultaneously or be asynchronously hydrogen or alkyl, M be Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or be protonated nitrogen base, and wherein m is 1,2,3 or 4;
Described fire retarding synergist is at least containing a NH
4 +ammonium salt, be selected from ammonium sulfate, aluminium ammonium sulfate, ammonium sulfate magnesium, ammonium sulfate zinc, ammonium sulfate calcium, ammonium sulfate iron, monoammonium sulfate, ammonium pyrosulfate, ammonium chloride, brometo de amonio, ammonium formiate, ammonium acetate, propionic acid ammonium, isopropyl acid ammonium, ammonium benzoate, toluylic acid ammonium, ammonium phthalate, m-phthalic acid ammonium, terephthalic acid ammonium, phenylpropionic acid ammonium, 2-methylphenyl acetic acid ammonium, 3-methylphenyl acetic acid ammonium, 4-methylphenyl acetic acid ammonium, 2-ethyl benzoate ammonium, 3-ethyl benzoate ammonium and/or 4-ethyl benzoate ammonium;
Described additive is char-forming agent and/or stablizer.
2. fire-retardant PS as claimed in claim 1, it is characterized in that, the weight part of described fire retardant is 5 ~ 25 parts; The weight part of fire retarding synergist is 20 ~ 40 parts.
3. fire-retardant PS as claimed in claim 1 or 2, it is characterized in that, the heat decomposition temperature of described fire retarding synergist is more than 180 DEG C.
4. fire-retardant PS as claimed in claim 1 or 2, is characterized in that, in described fire retardant, and R
1and R
2it can simultaneously or be asynchronously the alkyl of hydrogen or C1 ~ C6.
5. fire-retardant PS as claimed in claim 1 or 2, it is characterized in that, described fire retardant is hypo-aluminum orthophosphate, magnesium hypophosphite, calcium propionate, ferric hypophosphite, aluminum diethylphosphinate, diethyl phospho acid magnesium, diethyl phospho acid zinc, diethyl phospho acid calcium, diethyl phospho acid iron, dimethylphosphinic acid aluminium, dimethylphosphinic acid magnesium, dimethylphosphinic acid zinc, dimethylphosphinic acid calcium, dimethylphosphinic acid iron, dipropyl phospho acid aluminium, dibutyl phospho acid aluminium, diamyl phospho acid aluminium, dihexyl phospho acid aluminium, methylethyl phospho acid aluminium, methylpropylphosphinic acid aluminium, methyl butyl phospho acid aluminium, ethyl propyl phospho acid aluminium, ethyl-butyl phospho acid aluminium, monomethyl phospho acid aluminium, single ethylphosphinic acid aluminium, single propylphosphinic acid aluminium, monobutyl phospho acid aluminium, single amyl group phospho acid aluminium, single ethylhexyl hypophosphorous acid aluminium, monomethyl phospho acid magnesium, single ethylphosphinic acid magnesium, single propylphosphinic acid magnesium, monobutyl phospho acid magnesium, monomethyl phospho acid calcium, single ethylphosphinic acid calcium, single propylphosphinic acid calcium and/or monobutyl phospho acid calcium.
6. the preparation method of fire-retardant PS described in Claims 1 to 5 any one claim, is characterized in that, comprises the steps: said components to be mixed in proportion, extrudes and obtain at 180 ~ 230 DEG C.
7. the goods be made up of fire-retardant PS described in Claims 1 to 5 any one claim.
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Application publication date: 20130529 Assignee: GUANGZHOU KINGFA CARBON FIBER NEW MATERIAL DEVELOPMENT CO., LTD. Assignor: Mianyang Changxin New Material Development Co., Ltd. | Blonde Technology Co., Ltd Contract record no.: 2015440000877 Denomination of invention: Fire-retarding PS (Poly Styrene) as well as preparation method and product thereof Granted publication date: 20150701 License type: Exclusive License Record date: 20151224 |
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Address after: Ke Feng Lu Science City high tech Industrial Development Zone of Guangzhou City, Guangdong Province, No. 33 510663 Patentee after: Kingfa Technology Co., Ltd. Patentee after: SICHUAN KINGFA TECHNOLOGY DEVELOPMENT CO., LTD. Address before: Ke Feng Lu Science City high tech Industrial Development Zone of Guangzhou City, Guangdong Province, No. 33 510663 Patentee before: Kingfa Technology Co., Ltd. Patentee before: Mianyang Changxin New Material Development Co., Ltd. |