CN1651505A - Heat resistant smoke inhibiting polyvinyl chloride composition and its preparation method - Google Patents
Heat resistant smoke inhibiting polyvinyl chloride composition and its preparation method Download PDFInfo
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- CN1651505A CN1651505A CN 200410005193 CN200410005193A CN1651505A CN 1651505 A CN1651505 A CN 1651505A CN 200410005193 CN200410005193 CN 200410005193 CN 200410005193 A CN200410005193 A CN 200410005193A CN 1651505 A CN1651505 A CN 1651505A
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Abstract
A process for preparing the smoke-inhibiting refractory polyvinyl chloride composition features that the multiple elements componding technique is used to improve the high-temp resistance to toughness of PVC, and the two kinds of high-toughness and -rigidity materials are used as its modifier. Its product has excellent high-temp resistance, flame-retarding nature, smoke inhibition and weatherability.
Description
Technical field
The present invention relates to a kind of polychloroethylene composition and preparation method thereof, relate in particular to a kind of heat-resisting smoke-inhibiting PVC composition and preparation method thereof.
Background technology
Because requirements such as tame electrical article is good to thermotolerance, high rigidity, dimensional stability, anti-creeps, main at present good combination property, the engineering plastics acrylonitrile-butadiene-styrene copolymer (ABS) that surface gloss is high of adopting.But bad because of the ABS resin flame retardant resistance, weathering resistance is relatively poor, and cost is also higher, and therefore being necessary to develop novel material improves its flame retardant resistance and weathering resistance, and reduces cost.
Polyvinyl chloride (PVC) is a kind of output height, widely used general-purpose plastics, because of it has the advantage that flame retardant resistance is strong, dimensional stability good, chemical resistant properties is good and inexpensive, also has certain Application Areas in family expenses goods field.But also there are several major defects in PVC, and promptly poor processability, toughness and heat resisting temperature are low, and combustion fumes is poisonous etc., and these defectives have had a strong impact on the application of PVC in the family expenses field.
The PVC/ABS alloy, because of it has shock resistance, rigidity and stress cracking resistance preferably, and excellent in flame retardance, be used for making tame electrical articles such as televisor and telephone outer shell in a large number.This type of patent has disclosed Chinese patent CN1107487 on August 30 nineteen ninety-five " health flame-retardant ABS/PVC injection alloy ", the alloy system of disclosed Chinese patent CN1120563 on April 17 " fire-retardant PVC injection alloy " in 1996 and the above-mentioned patent disclosure of disclosed CN1191232 on August 26th, 1998 " the PVC/ABS alloy material of low ABS content " has resistance to impact shock and tensile strength preferably, what have also has certain flame retardant resistance or a thermotolerance, improved the PVC poor processability to a certain extent, defectives such as toughness and heat-drawn wire are low have flame retardant properties preferably than common PVC resin modified system, processing characteristics and shock resistance.But only use ABS resin to improving thermotolerance and the intensity of PVC, and be limited, so above-mentioned materials still exists a lot of defectives the improvement of the processing fluidity of material.At first, three pieces of patents all do not relate to the improvement to the system smoke suppressing, and we know, smoke suppressing is very important performance to household article, is directly connected to people's life and health; Secondly above-mentioned materials still exists thermostability deficiency, processing characteristics defect of bad, can not satisfy the needs of high temperature process moulding, has also limited its application on injection-molded items such as some thin-walleds, household article such as complex-shaped and precise electronic device; In addition, owing to the existence of the two keys of divinyl, the weather resistance of goods is relatively poor among the ABS, and preproduction is flavescence easily in use, and this also is the defective that the PVC/ABS alloy material is difficult to overcome.
Summary of the invention
The present invention is directed to the deficiency of above-mentioned patent interalloy system, a kind of heat-resisting smoke-inhibiting PVC composition is provided.That said composition is taken into account is heat-resisting, fire-retardant, press down the cigarette three efficacy, possesses good physical and mechanical properties, weathering resistance and moulding processability simultaneously, and with low cost, does not have lead stabilizer, has the feature of environmental protection preferably.The present invention also provides the preparation method of above-mentioned composition.
Heat-resisting smoke-inhibiting PVC composition provided by the invention comprises following component:
A. polyvinyl chloride (PVC) resin: mean polymerisation degree≤700 are preferably: mean polymerisation degree≤500 most preferably are mean polymerisation degree=300;
B. acrylonitrile-butadiene-styrene copolymer (ABS): melt mass flow rate 〉=2 are preferably: melt mass flow rate 〉=3.5 most preferably are melt mass flow rate=5;
C. styrene-acrylonitrile copolymer (SAN): melt mass flow rate 〉=2; Be preferably: melt mass flow rate 〉=3.5 most preferably are melt mass flow rate=5;
D. rare earth composite stabilizer: technical grade product;
E. the molybdenum class presses down fumicants: molybdenum content 〉=1%;
F. zinc borate: 〉=200 orders;
G. polyethylene wax: technical grade product;
H. glyceryl monostearate: technical grade product;
I. light calcium carbonate: 〉=300 orders;
J. chlorinatedpolyethylene: cl content 34-36%
The parts by weight of above each component are:
a:：70-30，b：0-50，c：5-60，d：3-6，e：1-10，
f：0-10，g：0.3-2，h：0.5-2，i：5-10，j：0-20；
At least contain a kind of among components b and the component j in the composition;
Said composition has following performance: flame retardant rating V
0, smoke density≤380, tensile strength 〉=40MPa, heat-drawn wire 〉=75 ℃, Vicat softening point 〉=92 ℃.
Composition of the present invention adopts polynary compounding technology to improve the heat-resisting and toughness defect of insufficient of PVC, and the material of selecting two types of toughness and rigidity for use improving flexible simultaneously, improves the thermotolerance of material as properties-correcting agent.The adding of ABS properties-correcting agent can strengthen PVC and can be toughness reinforcing, but thermotolerance and intensity to system increase limited, the adding of the 3rd component SAN is chosen in test thus, different requirements according to goods, can control the crisp tough degree of goods by SAN consumption in the adjusting prescription, the adding of SAN simultaneously can improve the system flowability, be beneficial to the injection moulding processing under the shear conditions, SAN also has the advantage of a uniqueness, owing to do not contain two keys in its molecular chain, has good weathering resistance, the life-time service nondiscoloration, effectively improved the weathering resistance of material, special in the prescription that does not use ABS properties-correcting agent, material reaches higher weather-proof grade.
The heat resisting temperature of modifier A BS, SAN component is higher, heat-drawn wire is more than 80 ℃, and the PVC heat-drawn wire adopts the properties-correcting agent component of ABS and SAN preparation only about 60 ℃, materials hot deformation temperature and Vicat softening point are obviously improved, and material thermal resistance obviously strengthens.
The PVC burning produces a large amount of dense smokes, therefore should improve the fire-retardant rank of alloy material makes it have good smoke suppressing again, select the inorganic fire-retarded smoke system that presses down of particularly outstanding zinc borate of good stability, not volatile, low toxicity, smoke elimination effect and molybdenum oxide class for use, can make material reach V
0The level flame retardant effect, and the amount of being fuming reduces greatly.
System is selected rare earth-stabilized system for use, and under the prerequisite that guarantees thermostability, farthest having reduced lead is the pollution of stabilising system to environment, compares with the organotin stabilising system simultaneously and has reduced cost.
The preparation method of the present composition may further comprise the steps:
A. component a and component d-j are put into high low speed mixing and blending machine group and stir, high-speed stirring mixing time 〉=10min wherein, temperature of charge 〉=100 ℃, discharging when stirring at low speed is cooled to temperature≤50 ℃;
B. behind material that will stir and components b, the c even blend with single screw rod or the granulation of incongruous double screw tablets press, temperature is 165 ℃-180 ℃.
The also available following preparation method's preparation of the present composition, this method may further comprise the steps:
A. component a and component d-j are put into high low speed mixing and blending machine group and stir, high-speed stirring mixing time 〉=10min wherein, temperature of charge 〉=100 ℃, discharging when stirring at low speed is cooled to temperature≤50 ℃;
B. the material that will stir is with single screw rod or the granulation of incongruous double screw tablets press, and temperature is 140 ℃-170 ℃, will get final product behind grain and components b that produce, the c even blend.
The present composition is heat-resisting, weather-proof, smoke suppressing is good, and the physical and mechanical properties height, good processability.Be suitable for the high temperature process moulding, especially be used in injection-molded items such as some thin-walleds, household article such as complex-shaped and precise electronic device thereof, saved production cost, have high economic benefit.
Shooting Technique is when utilizing the present composition to prepare injecting products: injection temperature 180-190 ℃, and 175 ℃ of cast gate temperature, injection pressure 70-80%, injection cycle 30-60S.
With embodiment effect of the present invention is described below, embodiment component concentration and performance are as shown in table 1, but can not think that the present invention only only limits to these embodiment.
Embodiment:
Embodiment adopts material and specification:
A. the mean polymerisation degree of polyvinyl chloride (PVC) RESINS: embodiment 3 is 600, and the mean polymerisation degree of embodiment 5 is 400.The mean polymerisation degree of remaining embodiment is 700;
B. acrylonitrile-butadiene-styrene copolymer: melt mass flow rate=3.2;
C. styrene-acrylonitrile copolymer: melt mass flow rate=3.5;
D. rare earth composite stabilizer: technical grade product;
E. the molybdenum class presses down fumicants: molybdenum content=3%;
F. zinc borate: technical grade product, 200 orders;
G. polyethylene wax: technical grade product;
H. glyceryl monostearate: technical grade product;
I. light calcium carbonate: 325 orders;
J. chlorinatedpolyethylene: cl content=35;
The preparation method of embodiment may further comprise the steps:
A. PVC and other auxiliary agent are put into high low speed mixing and blending machine group stirring, wherein high-speed stirring is mixed 12min, 110 ℃ of temperature of charge, discharging when stirring at low speed is cooled to 50 ℃;
B. behind material that will stir and ABS, the SAN even blend with single screw rod or the granulation of incongruous double screw tablets press, temperature is 170 ℃.
The composition properties testing method:
The test item examination criteria
Tensile strength GB/T 1040-1992
Notched Izod impact strength GB/T 1043-1993
Heat-drawn wire GB/T 1643-1979
Vicat softening point GB/T 1633-1979
Flame retardant resistance UL-94
Smoke density GB/T 8323-1987
Yellow index GB/T 2409-1980
Annotate: weathering resistance adopts the aging under field conditions (factors) yellow index assessment that (comprises sunshine, drenches with rain) after 60 days of sample.
Table 1. embodiment
| Project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Composition component (parts by weight) | |||||
| Polyvinyl chloride resin (a) | Part | ????70 | ????50 | ????40 | ????40 |
| ABS resin (b) | Part | ????25 | ????45 | ????30 | ????20 |
| SAN resin (c) | Part | ????5 | ????5 | ????30 | ????40 |
| Rare earth composite stabilizer (d) | Part | ????5 | ????4 | ????4 | ????4 |
| Zinc borate (e) | Part | ????5 | ????5 | ????5 | ????5 |
| The molybdenum class presses down fumicants (f) | Part | ????0 | ????5 | ????8 | ????5 |
| Polyethylene wax (g) | Part | ????0.6 | ????1 | ????1 | ????1 |
| Glyceryl monostearate (h) | Part | ????1 | ????0.5 | ????1 | ????1 |
| Light calcium carbonate (i) | Part | ????5 | ????5 | ????10 | ????5 |
| Chlorinatedpolyethylene (j) | Part | ????0 | ????0 | ????0 | ????0 |
| Composition properties | |||||
| Tensile strength | ??MPa | ????47 | ????43 | ????49 | ????52 |
| Notched Izod impact strength | ??KJ/m ?? 2 | ????14 | ????17 | ????9 | ????7 |
| Heat-drawn wire | ??℃ | ????75 | ????77 | ????79 | ????83 |
| Vicat softening point | ??℃ | ????93 | ????94 | ????97 | ????101 |
| Flame retardant resistance | ????V 0 | ????V 0 | ????V 0 | ????V 0 | |
| Smoke density | ????380 | ????330 | ????350 | ????360 | |
| 60 days yellow indexes of weather aging | ????26 | ????29 | ????27 | ????26 | |
Continuous table 1. embodiment
| Project | Unit | Embodiment 5 | Embodiment 6 | Comparative Examples 1 | Comparative Examples 2 |
| Composition component (parts by weight) | |||||
| Polyvinyl chloride resin (a) | Part | ??50 | ??40 | ??50 | ??100 |
| ABS resin (b) | Part | ??0 | ??0 | ??54.5 | ??4 |
| SAN resin (c) | Part | ??50 | ??60 | ??0 | ??0 |
| Rare earth composite stabilizer (d) | Part | ??4 | ??4 | (2.0 organotin) | (2.0 lead salt) |
| Zinc borate (e) | Part | ??8 | ??8 | 3 (clorafins) | ??0 |
| The molybdenum class presses down fumicants (f) | Part | ??0 | ??0 | ??0 | ??0 |
| Polyethylene wax (g) | Part | ??1 | ??1 | ??3.0 | (1.6 stearic acid) |
| Glyceryl monostearate (h) | Part | ??1 | ??1 | (0.4 stearic acid) | (1.5 stearate) |
| Light calcium carbonate (i) | Part | ??5 | ??5 | ??0 | ??18 |
| Chlorinatedpolyethylene (j) | Part | ??8 | ??12 | ??2.5 | ??0 |
| Composition properties | |||||
| Tensile strength | ??MPa | ??55 | ??58 | ??37 | ??53.9 |
| Notched Izod impact strength | ??KJ/m 2 | ??6 | ??7 | ??22 | ??16.3 |
| Heat-drawn wire | ??℃ | ??81 | ??82 | ??77 | ??75.5 |
| Vicat softening point | ??℃ | ??102 | ??104 | ||
| Flame retardant resistance | ??V 0 | ??V 0 | ??V 0 | ||
| Smoke density | ??380 | ??370 | |||
| 60 days yellow indexes of weather aging | ??19 | ??18.6 | |||
Claims (9)
1. heat-resisting smoke-inhibiting PVC composition comprises following component:
A. polyvinyl chloride (PVC) RESINS: mean polymerisation degree≤700;
B. acrylonitrile-butadiene-styrene copolymer: melt mass flow rate 〉=2g/10min;
C. styrene-acrylonitrile copolymer: melt mass flow rate 〉=2g/10min;
D. rare earth composite stabilizer: technical grade product;
E. zinc borate: technical grade product, 〉=200 orders;
F. the molybdenum class presses down fumicants: molybdenum content 〉=1%;
G. polyethylene wax: technical grade product;
H. glyceryl monostearate: technical grade product;
I. light calcium carbonate: 〉=300 orders;
J. chlorinatedpolyethylene: cl content 34%-36%
The parts by weight of above each component are:
a：：70-30，b：0-50，c：5-60，d：3-6，e：1-10，
f：0-10，g：0.3-2，h：0.5-2，i：5-10，j：0-20；
At least contain a kind of among components b and the component j in the composition;
Said composition has following performance: flame retardant rating V
0, smoke density≤380, tensile strength 〉=40MPa, heat-drawn wire 〉=75 ℃, Vicat softening point 〉=92 ℃.
2. as claim 1 described composition, it is characterized by: the mean polymerisation degree of component a≤500.
3. as claim 1 described composition, it is characterized by: the mean polymerisation degree of component a is 300.
4. as claim 1 described composition, it is characterized by: the melt mass flow rate of component b 〉=3.5.
5. as claim 4 described compositions, it is characterized by: the melt mass flow rate of component b=5.
6. as one of claim 1 described composition, it is characterized by: the melt mass flow rate of component c 〉=3.5.
7. as claim 1 described composition, it is characterized by: the melt mass flow rate of component c=5.
8. as preparation of compositions method as described in the claim 1-7, may further comprise the steps:
A. component a and component d-j are put into high low speed mixing and blending machine group and stir, high-speed stirring mixing time 〉=10min wherein, temperature of charge 〉=100 ℃, discharging when stirring at low speed is cooled to temperature≤50 ℃;
B. behind material that will stir and components b and the amount of component b even blend with single screw rod or the granulation of incongruous double screw tablets press, temperature is 165 ℃-180 ℃.
9. as preparation of compositions method as described in the claim 1-7, may further comprise the steps:
A. component a and component d-j are put into high low speed mixing and blending machine group and stir, high-speed stirring mixing time 〉=10min wherein, temperature of charge 〉=100 ℃, discharging when stirring at low speed is cooled to temperature≤50 ℃;
B. the material that will stir is with single screw rod or the granulation of incongruous double screw tablets press, and temperature is 140 ℃-170 ℃, gets final product behind the grain produced and components b and the amount of component b even blend.
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| CNB2004100051936A CN100415819C (en) | 2004-02-07 | 2004-02-07 | Heat resistant smoke inhibiting polyvinyl chloride composition and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100051936A CN100415819C (en) | 2004-02-07 | 2004-02-07 | Heat resistant smoke inhibiting polyvinyl chloride composition and its preparation method |
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| CN1651505A true CN1651505A (en) | 2005-08-10 |
| CN100415819C CN100415819C (en) | 2008-09-03 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360698A (en) * | 2012-03-31 | 2013-10-23 | 中国石油化工股份有限公司 | Inflaming-retarding and antistatic high-strength polyvinyl chloride tube stock composition |
| CN103387718A (en) * | 2012-05-08 | 2013-11-13 | 合肥杰事杰新材料股份有限公司 | PVC/ABS alloy and preparation method thereof |
| CN106280081A (en) * | 2016-08-08 | 2017-01-04 | 陶如意 | A kind of micro crystal graphite modified PVC pipeline and preparation method thereof |
| CN106280080A (en) * | 2016-08-08 | 2017-01-04 | 陶如意 | A kind of fire-retardant low free chlorine PVC pipeline and preparation method thereof |
| CN107540988A (en) * | 2017-10-12 | 2018-01-05 | 钱艺博 | One kind suppression cigarette base polyvinyl chloride material and preparation method thereof |
| CN108296420A (en) * | 2017-10-27 | 2018-07-20 | 柳州市柳晶科技股份有限公司 | A kind of 3D printing precoated sand and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333305A (en) * | 2000-07-07 | 2002-01-30 | 江苏琼花集团有限公司 | Fire-resistant smoke-inhibiting PVC package sheet material |
| CN1123597C (en) * | 2000-10-27 | 2003-10-08 | 陈伟瑜 | Fire-retardant and smoke-inhibiting type polyvinyl-chloride/calcium carbonate composite material and its prepn. method |
-
2004
- 2004-02-07 CN CNB2004100051936A patent/CN100415819C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360698A (en) * | 2012-03-31 | 2013-10-23 | 中国石油化工股份有限公司 | Inflaming-retarding and antistatic high-strength polyvinyl chloride tube stock composition |
| CN103387718A (en) * | 2012-05-08 | 2013-11-13 | 合肥杰事杰新材料股份有限公司 | PVC/ABS alloy and preparation method thereof |
| CN106280081A (en) * | 2016-08-08 | 2017-01-04 | 陶如意 | A kind of micro crystal graphite modified PVC pipeline and preparation method thereof |
| CN106280080A (en) * | 2016-08-08 | 2017-01-04 | 陶如意 | A kind of fire-retardant low free chlorine PVC pipeline and preparation method thereof |
| CN107540988A (en) * | 2017-10-12 | 2018-01-05 | 钱艺博 | One kind suppression cigarette base polyvinyl chloride material and preparation method thereof |
| CN108296420A (en) * | 2017-10-27 | 2018-07-20 | 柳州市柳晶科技股份有限公司 | A kind of 3D printing precoated sand and preparation method thereof |
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|---|---|
| CN100415819C (en) | 2008-09-03 |
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