CN103073807A

CN103073807A - Low-cost medium-flow high-weather-proof environment-friendly brominated flame retardant ASA material as well as preparation method and application thereof

Info

Publication number: CN103073807A
Application number: CN2013100223378A
Authority: CN
Inventors: 汪炉林; 郭涛; 王林; 程庆; 王亮; 叶晓光; 袁绍彦
Original assignee: MIANYANG CHANGXIN NEW MATERIAL DEVELOPMENT Co Ltd; Kingfa Science and Technology Co Ltd
Current assignee: MIANYANG CHANGXIN NEW MATERIAL DEVELOPMENT Co Ltd; Kingfa Science and Technology Co Ltd
Priority date: 2013-01-22
Filing date: 2013-01-22
Publication date: 2013-05-01

Abstract

The invention discloses a low-cost medium-flow high-weather-proof environment-friendly brominated flame retardant ASA (acrylonitrile styrene acrylate) material, which comprises the following components in parts by weight: 15-40 parts of ASA resin, 30-60 parts of styrene-acrylonitrile resin, 8-12 parts of environment-friendly brominated flame retardant, 5-20 parts of chlorinated polyethylene and 2-6 parts of novel environment-friendly flame retardant synergist. A preparation method for the ASA material comprises the steps as follows: adding the components into a high-speed mixer in sequence according to the proportion for uniformly mixing, and adding a mixture into a double screw extruder for mixing, extruding, pulling, water-cooling and dicing to obtain the ASA material. According to the ASA material, the addition amount of the flame retardant is lower than that of other conventional flame-retardant system by more than 1/3; through the test, the flame retardant level reaches UL94@3.0-1.0 mm V-0, the impact intensity is kept more than 10 kJ/m<2>, the melting index exceeds 35 g/10 min, the weather-proof performance is excellent, and the other mechanical performance is balanced; the preparation method is simple and easy to implement; and the ASA material is easy to process and is suitable for popularization and application in the fields of outdoor electronic products and the like.

Description

The high weather resistance environmental protection bromine that flows in a kind of low cost is flame-retardant ASA material and preparation method thereof and application

Technical field

The invention belongs to polymeric material field, be specifically related to a kind of flame-retardant ASA material, preparation method and application that the high weather resistance environmental protection bromine that particularly flows in a kind of low cost is flame-retardant ASA material.

Background technology

The ternary graft copolymer that the ASA resin is comprised of vinylbenzene, acrylate, vinyl cyanide is take polyacrylic ester as main chain, with the non-crystalline polymer of vinyl cyanide, styrene monomer graft copolymerization formation.ASA realized suitability for industrialized production first by BASF AG of Germany in 1962, FDAC changes into and also realized industrialization subsequently.

Because the ASA resin adopted the polyacrylic ester without double bond structure to substitute polybutadiene rubber among the ABS, therefore become one of best kind of weathering resistance in the plastics, its weathering resistance is higher more than 10 times than ABS resin.But itself also belongs to inflammable material the ASA resin, and is therefore the same with ABS resin, when being used for electronic and electrical equipment, need to carry out flame-retardant modified, to reach the fire safety service requirements.The mixture that is fire retarding synergist by adding the bromide fire retardant that surpasses more than 20% and antimony to the method flame-retardant modified the most effective, that cost is minimum of thermoplastic's resin at present.Because ASA resin itself is because of its most of outdoor field of electronics that are used for that have excellent weather resistance, therefore the affiliation that adds of so many bromide fire retardant causes its weathering resistance deterioration serious, has lost its excellent weather resistance characteristics.Such as Chinese patent CN101397391 tetrabromo-bisphenol and antimonous oxide are disclosed as the fire retardant of the flame-retardant modified usefulness of ASA resin, but the weathering resistance of tetrabromo-bisphenol and heat-resistant stability are all relatively poor, it is added to the weathering resistance that can cause the ASA resin in the ASA resin and reduces thermostability decline.Chinese patent CN101765635A discloses the ASA modified resin of brominated epoxy as fire retardant, because weathering resistance and the heat-resistant stability of brominated epoxy all are better than tetrabromo-bisphenol, but the brominated epoxy resin softening temperature only has about 90 degree, in the blending extrusion process, easily lump, affect metering system, and and then affect fire-retardant stability and the mechanical property of the finished product.Chinese patent CN102002203A discloses three (three-bromophenyl) cyanurate fire retardant, and to be applied to ASA flame-retardant modified, this fire retardant has kept the physical strength of ASA resin preferably, weathering resistance and thermostability all are better than the flame-proof ABS product of identical flame-retardant system, but because the total addition level of itself and Sb system fire retardant is about 20%, so many addition causes weathering resistance that to a certain degree deterioration is arranged, and the flowability of this system is general, is not optimal selection in forming thin-walled and large size product.Simultaneously, because the price comparison of ASA resin own is high, the adding of so many bromo-antimony composite flame-retardant agent causes the further raising of its cost, is difficult to apply in market.

Summary of the invention

For the shortcoming that overcomes prior art with not enough, primary and foremost purpose of the present invention be to provide flow in a kind of, the environmental protection bromine of high weather-proof, high-performance, handling ease is flame-retardant ASA material.

Another object of the present invention is to provide above-mentioned environmental protection flame retardant ASA material preparation method.

The present invention is achieved by the following technical solutions:

The high weather resistance environmental protection bromine that flows in a kind of low cost is flame-retardant ASA material, counts by weight, comprises following component:

ASA resin 15-40 part

Styrene-acrylonitrile resin 30-60 part

Environmental protection bromide fire retardant 8-12 part

Chlorinatedpolyethylene 5-20 part

Novel environment friendly fire retarding synergist 2-6 part

Described ASA resin is for being the acrylonitrile-styrene-acrylic ester terpolymer.

Described environmental protection bromide fire retardant is brominated epoxy resin.

The compound that described novel environment friendly fire retarding synergist is comprised of antimony compounds, inorganic powder and ultra-high molecular weight polysiloxane, the weight percentage of antimony compounds is 20-80% in this compound.

Described antimony compounds is antimonous oxide, colloidal antimony pentoxide, sodium antimonate, butter of antimony, antimony pentachloride, one or more composite the forming in phosphorous acid antimony, polyphosphoric acid antimony, the complexing antimony.

Described inorganic powder is one or more the mixture in talcum powder, titanium dioxide, zinc sulfide white, magnesiumcarbonate, barium sulfate, marble dust, mica powder, natural silica, wollastonite powder, kaolin or the Feldspar Powder.

The weight-average molecular weight of described ultra-high molecular weight polysiloxane 〉=30,000, when temperature is 25 ℃, its viscosity 〉=500mPas.

Described ultra-high molecular weight polysiloxane is one or more the mixture in methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amide group polysiloxane, epoxy group(ing) polysiloxane, isobutyl-polysiloxane, styryl polysiloxane or the ring texture polysiloxane.

Material of the present invention also comprises 0.1-0.3 part anti-dripping agent, 0.1-2 part dispersion agent, 0-1 part oxidation inhibitor, 0-1 part photostabilizer or 0-5 part processing aid.

Described anti-dripping agent is tetrafluoroethylene.

Described dispersion agent is the stearic acid dispersion agent.

Described oxidation inhibitor is the mixture that Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant form.

Described photostabilizer is the mixture of benzophenone, benzotriazole category, triazines, poly-one or more in the fine class of propylene, Oxamides and the hindered amines.

Described processing aid is one or more the mixture in stearylamide series lubricant agent, silicone oil and the white mineral oil.

The preparation method that the high weather resistance environmental protection bromine that flows in the low cost of the present invention is flame-retardant ASA material comprises the steps:

A, each component raw material was fully mixed 10-60 minute at high-speed mixer by proportioning;

B, said mixture is transported in the twin screw extruder through the pay-off of delicate metering, each of forcing machine section extruder temperature is controlled between 180 ~ 230 ℃, the length-to-diameter ratio of twin screw extruder is 25 ~ 40, screw speed is 200-800 rev/min, the shearing of screw rod, mixing and carry under, material is able to abundant fusing, compound, obtains flame-retardant ASA material through extruding pelletization, drying again.

The high weather resistance environmental protection bromine that flows in the low cost of the present invention is the outdoor large thin-walled electronic apparatus series products that flame-retardant ASA material can be widely used in the high weather-proof requirement of needs, is adapted at applying on the market.

The present invention compared with prior art has following beneficial effect:

1) mobile high weather resistance environmental protection bromine is flame-retardant ASA material in the low cost of the present invention, and the addition of its fire retardant is less than at present more than 1/3 of other flame-retardant system consumption;

2) mobile high weather resistance environmental protection bromine is the test of flame-retardant ASA material process in the low cost of the present invention, and its flame retardant rating reaches UL941.0-3.0mmV-0, and shock strength then remains on 10kJ/m ²Above, melt index under all other mechanical property equilibriums, has certain weathering resistance more than 35g/10min.

3) mobile high weather resistance environmental protection bromine is that the flame-retardant ASA material preparation method is simple in the low cost of the present invention, handling ease, its cost is suitable even lower with the present flame-proof ABS that generally uses simultaneously, therefore is adapted at outdoor large thin-gage goods field and applies.

Embodiment

Further specify the present invention below by embodiment, following examples are the better embodiment of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.

Now embodiment and the used starting material of Comparative Examples are done following explanation, but are not limited to these materials:

The ASA resin is selected the A600N of Japanese UMG;

Styrene-acrylonitrile resin is selected the NF2200 of platform;

ABS resin is selected the AG15A1 of Taiwan

Environmental protection macromolecule amount bromide fire retardant is selected the CN-3384 of big lake chemical industry;

Tetrabromo-bisphenol is selected the FR-1524 of Israel Dead Sea bromine company;

The CXB-714C that brominated epoxy resin selects Korea S's space to advance;

Brominated triazine is selected the FR-245 of Israel Dead Sea bromine company;

Chlorinated polyethylene resin is selected the CPE 2135 of Shandong AsiaSat company;

Anti-dripping agent is selected the SN80-SA7 of Guangzhou entropy energy company;

Dispersion agent selects reason to grind the S-74 of company and the EBS of Dow Chemical company;

Antimony compounds is selected the S-05N of the sharp antimony industry of Yunnan wood company limited;

Photostabilizer is selected Milan, Nanjing chemical industry photostabilizer HS-770;

Oxidation inhibitor is selected pentaerythritol ester 1010 and the phosphorous acid ester 168 of gas Ba Jinghua;

Processing aid is selected No. 70 white oils of white mineral oil of Liaoning AoKe Chemical Co., Ltd;

Calcium stearate BS-3818 obtains can buying on the market.

The present invention prepares the used plant and instrument of composition to be had:

The flame-retardant modified used twin screw extruder of thermoplastics is the SHJ-30 that is produced by Nanjing Rhea superpolymer equipment company limited.

The injection moulding machine that flame-proofed thermoplastic plastic testing batten adopts is the B-920 type by day injection moulding machine company limited production of sea, Zhejiang.

The instrument that the test melt flow rate (MFR) is used is the ZR21452 Melt Flow Rate Measurer that beautiful this company limited of secret service industry system (China) produces.

The impact experiment machine that the test shock strength is used is the T92 type that U.S. Tinius Olsenis company produces.

The universal testing machine that test tensile strength is used is the H10K-S that Hounsfield company produces.

The UL-94 vertical combustion instrument that the test flame retardant rating uses is U.S. ATLAS HVUL-2.

That the test weathering resistance is used is the xenon lamp aging case JN-HQLH-1581 of UL company.

Test atmospheric exposure test condition: black mark temperature: 65 ℃; Relative humidity: 65%; Irradiance: 0.50W/m ²340nm; Loop cycle: continuous illumination, 102min does not spray, the 18min spray; Test period: 800h

The preparation of novel environment friendly fire retarding synergist XX:

With talcum powder 68 gram, dimethyl polysiloxane 12 grams, antimonous oxide 20 grams high-speed mixer and mixing 20 minutes, can be prepared novel environment friendly fire retarding synergist XX ₁, the weight-average molecular weight of described dimethyl polysiloxane is 30000, its viscosity is 500PaS.

With talcum powder 18 gram, dimethyl polysiloxane 2 grams, antimonous oxide 80 grams high-speed mixer and mixing 20 minutes, can be prepared novel environment friendly fire retarding synergist XX ₂, the weight-average molecular weight of described dimethyl polysiloxane is 30000, its viscosity is 500PaS.

With talcum powder 44 gram, dimethyl polysiloxane 6 grams, antimonous oxide 50 grams high-speed mixer and mixing 20 minutes, can be prepared novel environment friendly fire retarding synergist XX ₃, the weight-average molecular weight of described dimethyl polysiloxane is 30000, its viscosity is 500PaS.

The high weather resistance environmental protection bromine that flows in the low cost is the flame-retardant ASA material preparation:

At first each component of each Comparative Examples/embodiment is successively added in the high-speed mixer by proportioning and evenly mixes, then said mixture is sent into mixing in the twin screw extruder, extrude, tie rod, water-cooled, pelletizing; Wherein, the length-to-diameter ratio of twin screw extruder is 25-40; The barrel Temperature Setting is: 180 ℃ of district's temperature, 190 ℃ of two district's temperature, 200 ℃ of three district's temperature, 210 ℃ of four district's temperature, 220 ℃ of five district's temperature, 220 ℃ of six district's temperature, 220 ℃ of seven district's temperature, 220 ℃ of eight district's temperature, 220 ℃ of nine district's temperature, 220 ℃ of ten district's temperature, 230 ℃ of head temperatures; Screw speed is 200-800 rev/min.Above-mentioned each routine prepared plastic particles is injection molded into the standard batten of test usefulness by standard size, and carries out each performance test by testing standard; The performance test data of each routine sample sees Table 1-3.

The properties testing standard

Test event	Unit	Testing standard
			Tensile strength TS	Mpa	ISO 527
Elongation at break EL	%	ISO 527
			Socle girder notched Izod impact strength NIS	kJ/m ²	ISO 180, and the breach type is A type breach
Flexural strength FS	Mpa	ISO 178
			Modulus in flexure FM	Mpa	ISO 178
Melting index MI	10g/min	ISO 1133
			Burning UL94	class	UL94
Weathering resistance WR	?	GB/T 16422.2
			Heat-drawn wire H.D.T.	℃	ISO 75

Concrete proportioning and the performance test data of each component in table 1 embodiment and the Comparative Examples

	Comparative Examples 1	Comparative Examples 2	Comparative Examples 3	Comparative Examples 4	Comparative Examples 5	Comparative Examples 6	Embodiment 1	Embodiment 2	Embodiment 3
										A600N	25	25	25	25	25	?	25	25	25
AS	65	47	47	47	47	?	47	49	50
										AG15A1	?	?	?	?	?	72	?	?	?
FR-1524	?	15	?	?	?	?	?	?	?
										CXB-714C	?	?	15	?	?	15	12	10	8
FR-245	?	?	?	15	?	?	?	?	?
										CN-3384		?			15	?			?
CPE 2135	10	10	10	10	10	10	10	10	10
										XX ₁						?	6	5	5
S-05N	?	3	3	3	3	3	?	?	?
										SN80-SA7	?	0.1	0.1	0.1	0.1	0.1	0.1	0.2	0.3
S-74	?	0.5	0.5	0.5	0.5	0.5	0.5	1	2
										Antioxidant 1010+168	0.4	0.4	0.4	0.4	0.4	0.4	0.4	0.6	1
HS-770	0.5	0.5	0.5	0.5	0.5	0.1	0.1	0.7	1
										BS 3818+70 white oil	1	1	1	1	1	1	1	3	5
TS	43	40	38	38	42	38	37	38	39
										EL	5	5	5	5	5	5	5	5	5
NIS	16	10	7	12	12	10	12	12	13
										FS	62	65	63	66	66	60	59	60	61
FM	2200	2500	2300	2500	2450	2050	2050	2100	2120
										MI	18	45	39	30	14	35	47	45	43
UL941.0mm	/	V-0	V-0	V-0	V-0	V-0	V-0	V-0	/
										UL941.5mm	/	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
UL942.0mm	/	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
										UL942.5mm	/	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
UL943.0mm	/	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
										H.D.T	82	74	78	77	80	78	79	79	80
WR	3.58	15.51	9.17	9.05	7.35	20.06	7.42	6.51	5.49

Concrete proportioning and the test performance thereof of each component among each embodiment of table 2

	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11
									A600N	15	20	25	30	35	40	39	34
AS	55	50	45	40	35	30	40	40
									CXB-714C	10	10	10	10	10	10	10	10
CPE 2135	14	14	14	14	14	14	5	10
									XX ₂	5	5	5	5	5	5	5	5
SN80-SA7	0.1	0.1	0.2	0.3	0.1	0.1	0.2	0.3
									S-74	0.5	0.5	1	2	0.5	0.5	1	2
Antioxidant 1010+168	0.4	0.4	0.6	1	0.4	0.4	0.6	1
									HS-770	0.5	0.1	0.7	1	0.5	0.1	0.7	1
BS 3818+70 white oil	1	1	1	1	1	1	1	1
									TS	36	36	36	35	35	35	38	37
EL	5	5	5	5	5	5	5	5
									NIS	14	15	16	17	18	19	12	14
FS	58	57	57	57	57	57	60	59
									FM	1980	1950	1900	1850	1850	1800	2050	2000
MI	42	40	39	37	36	35	42	40
									UL941.0mm	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
UL941.5mm	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
									UL942.0mm	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
UL942.5mm	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
									UL943.0mm	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
H.D.T	78	78	78	77	77	77	78	78
									WR	4.31	4.96	5.33	6.44	7.22	7.79	8.00	7.88

Concrete proportioning and the test performance thereof of each component among each embodiment of table 3

	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	Embodiment 17	Embodiment 18	Embodiment 19	Embodiment 20
										A600N	29	24	25	25	25	25	25	25	15
AS	40	40	50	50	50	50	50	50	60
										CXB-714C	10	10	12	11	11	10	9	8	8
CPE 2135	15	20	10	10	10	10	10	10	10
										XX ₃	5	5	2	2	3	4	5	6	6
SN80-SA7	0.3	0.3	0.2	0.2	0.2	0.2	0.2	0.2	0.2
										S-74	2	2	1	1	1	1	1	1	1
Antioxidant 1010+168	1	1	0.6	0.6	0.6	0.6	0.6	0.6	0.6
										HS-770	1	1	0.7	0.7	0.7	0.7	0.7	0.7	0.7
BS 3818+70 white oil	1	1	1	1	1	1	1	1	1
										TS	36	34	39	39	39	39	38	38	40
EL	5	5	5	5	5	5	5	5	5
										NIS	17	19	9	10	12	13	14	17	12
FS	57	56	60	60	60	59	59	60	60
										FM	1850	1750	2100	2150	2100	2050	2010	2020	2050
MI	40	38	45	44	44	55	57	57	59
										UL941.0mm	V-0	V-0	/	/	/	/	/	V-0	V-0
UL941.5mm	V-0	V-0	/	/	/	/	V-0	V-0	V-0
										UL942.0mm	V-0	V-0	/	/	/	V-0	V-0	V-0	V-0
UL942.5mm	V-0	V-0	/	/	V-0	V-0	V-0	V-0	V-0
										UL943.0mm	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
H.D.T	77	77	79	78	78	78	78	78	78
										WR	7.89	7.16	7.42	8.80	9.12	9.76	9.99	10.18	7.62

Performance comparison by above-described embodiment and Comparative Examples can be found out, by adding suitable species and properly mixed fire retardant and novel environment friendly fire retarding synergist thereof, the ASA material has excellent flame retardant properties and higher flowability, mechanical property, simultaneously, compare with flame-proof ABS, its weathering resistance improves more than 1 times under the same terms.

Claims

1. the high weather resistance environmental protection bromine that flows in the low cost is flame-retardant ASA material, it is characterized in that meter by weight comprises following component:

ASA resin 15-40 part

Styrene-acrylonitrile resin 30-60 part

Environmental protection bromide fire retardant 8-12 part

Chlorinatedpolyethylene 5-20 part

Novel environment friendly fire retarding synergist 2-6 part

Wherein, described environmental protection bromide fire retardant is brominated epoxy resin.

2. the high weather resistance environmental protection bromine that flows in the low cost according to claim 1 is flame-retardant ASA material, it is characterized in that, the compound that described novel environment friendly fire retarding synergist is comprised of antimony compounds, inorganic powder and ultra-high molecular weight polysiloxane, the weight percentage of antimony compounds is 20-80% in this compound.

3. the high weather resistance environmental protection bromine that flows in the low cost according to claim 2 is flame-retardant ASA material, it is characterized in that, described antimony compounds is antimonous oxide, colloidal antimony pentoxide, sodium antimonate, butter of antimony, antimony pentachloride, one or more composite the forming in phosphorous acid antimony, polyphosphoric acid antimony, the complexing antimony.

4. the high weather resistance environmental protection bromine that flows in the low cost according to claim 2 is flame-retardant ASA material, it is characterized in that, described inorganic powder is one or more the mixture in talcum powder, titanium dioxide, zinc sulfide white, magnesiumcarbonate, barium sulfate, marble dust, mica powder, natural silica, wollastonite powder, kaolin and the Feldspar Powder.

5. the high weather resistance environmental protection bromine that flows in the low cost according to claim 2 is flame-retardant ASA material, it is characterized in that, and the weight-average molecular weight of described ultra-high molecular weight polysiloxane 〉=30,000, when temperature is 25 ℃, its viscosity 〉=500mPas.

6. the high weather resistance environmental protection bromine that flows in the low cost according to claim 2 is flame-retardant ASA material, it is characterized in that, described ultra-high molecular weight polysiloxane is one or more the mixture in methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amide group polysiloxane, epoxy group(ing) polysiloxane, isobutyl-polysiloxane, styryl polysiloxane or the ring texture polysiloxane.

7. the high weather resistance environmental protection bromine that flows in the low cost according to claim 1 is flame-retardant ASA material, it is characterized in that, also comprises 0.1-0.3 part anti-dripping agent, 0.1-2 part dispersion agent, 0-1 part oxidation inhibitor, 0-1 part photostabilizer or 0-5 part processing aid.

8. the high weather resistance environmental protection bromine that flows in the low cost according to claim 7 is flame-retardant ASA material, it is characterized in that, described anti-dripping agent is tetrafluoroethylene; Described dispersion agent is the stearic acid dispersion agent; Described oxidation inhibitor is the mixture that Hinered phenols primary antioxidant and phosphorous acid esters auxiliary anti-oxidant form; Described photostabilizer is the mixture of benzophenone, benzotriazole category, triazines, poly-one or more in the fine class of propylene, Oxamides and the hindered amines; Described processing aid is one or more the mixture in stearylamide series lubricant agent, silicone oil and the white mineral oil.

9. the preparation method that the high weather resistance environmental protection bromine that flows in each described low cost of claim 1-8 is flame-retardant ASA material is characterized in that, comprises the steps:

10. the high weather resistance environmental protection bromine that flows in each described low cost of claim 1-8 is the out of doors application in the field of electronics of flame-retardant ASA material.