CN104987436A - Chlorinated polyethylene for PVG whole core fire resistant belt, preparation method and application thereof - Google Patents
Chlorinated polyethylene for PVG whole core fire resistant belt, preparation method and application thereof Download PDFInfo
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- CN104987436A CN104987436A CN201510487909.9A CN201510487909A CN104987436A CN 104987436 A CN104987436 A CN 104987436A CN 201510487909 A CN201510487909 A CN 201510487909A CN 104987436 A CN104987436 A CN 104987436A
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Abstract
The invention discloses chlorinated polyethylene for a PVG whole core fire resistant belt, a preparation method and an application thereof. The chlorinated polyethylene comprises the raw materials of 18-26 parts of high density polyethylene, 500-600 parts of industrial pure water, 0.075-0.1 part of initiating agents, 0.15-0.25 part of emulsifying agents and 0.5-0.8 part of dispersing agents. Compared with the prior art, the chlorinated polyethylene has the advantages that the chlorination technology of a two-stage method and heat treatment is adopted, chlorination is performed below the melting point of the raw material HDPE until the chlorine content is 10-25 percent, and chlorine pumping is stopped; then the temperature is increased above 2 DEG C of the initial melting point of the HDPE, and heat treatment is performed for 40 minutes; the temperature is lowered near the malcrystalline melting point, chlorine is pumped to be reacted until the specified chlorine content 36 percent is achieved, and therefore CPE products with the better mechanical strength and the better rubber elasticity are prepared. According to the chlorinated polyethylene for the PVG whole core fire resistant belt, the preparation method and the application thereof, the prepared products successfully replace 50 percent of chemigum, and the prepared PVG whole core fire resistant belt has the excellent in performance.
Description
Technical field
The invention belongs to chlorinatedpolyethylene preparation field, be specifically related to a kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, preparation method and application thereof.
Background technology
Conveying belt is the main tool of underground coal mine conveying coal, because traditional rubber conveyer belt is inflammable substance, the requirement of underground flame retardant can not be met, therefore, forbid use of going into the well, fire retarding conveying band is easily accomplished fire-retardant and antistatic, and has again waterproof, protection against the tide, anti tear, lightweight, less cost of power, is thus widely used at countries in the world underground coal mine.At present, unitary-core flame-resistant conveying belt is simple with its structure, and transmission is convenient, and not by distance limit, easily adjust replacing, the advantages such as safety performance is good, have become the main conveyance of underground coal mine.
Unitary-core flame-resistant conveying belt after fully flooding PVC paste resin, plastifies into closely knit framework material by whole belt core, then through up and down coated with rubber wear-resisting layer, it is high that it has intensity compared with duck conveyor belt, wear-resistant, fire-retardant, the features such as anti tear.Rubber cover is the surface material of conveying belt; it is coated with belt carcass completely; play protection belt carcass; extend the effect in conveying belt work-ing life; tectum determines the transportation characterization of conveying belt, impact property, antiwear characteristic; corrosion resistance characteristic and fire-retardant, antistatic property etc., it is formed through high temperature plasticizing or compression molding.
Unitary-core flame-resistant conveying belt can be divided into PVC type and PVG type.In PVC type, lower caldding layer is PVC lid glue, one side glue > 0.8mm, and the upper and lower rubber cover of PVG type is PVC and paracril (NBR) and use, and one side thickness is 1.5mm-4.5mm.
The material of main part of PVG unitary-core flame-resistant conveying belt rubber cover is PVC and paracril (NBR), be applicable to the environment that transport inclination angle is less than 20 degree, it has more excellent gradeability than PVC rubber cover simultaneously, larger traffic capacity, PVC unitary-core flame-resistant conveying belt poor flexibility can be improved, the shortcomings such as not wear-resisting and weathering resistance is poor.
NBR is famous with the oil resistance of its excellence, also has enough good physical and mechanical properties and process industrial art performance simultaneously; But its ozone resistance and aging resistance are inferior a little, pure glue intensity is very low, and flame retardant properties is general, and in the course of processing smell weight, larger to the healthy harm of operator.
Study a kind of products substitution NBR with excellent fire-retardant and ozone resistance and good anti tear and tensile property necessary.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, partially or completely can substitute NBR, meet the requirement of PVG unitary-core flame-resistant conveying belt, improve the over-all properties of PVG unitary-core flame-resistant conveying belt.
Present invention also offers a kind of preparation method of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, by two-stage method+thermal treatment chloridization process, manufacture obtains the chlorinatedpolyethylene with higher elongation at break, meets the requirement of PVG unitary-core flame-resistant conveying belt.
Present invention also offers a kind of application of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, as the application of PVG unitary-core flame-resistant conveying belt properties-correcting agent, substitute paracril, the excellent performance of the PVG unitary-core flame-resistant conveying belt of preparation.
A kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene provided by the invention, comprises the raw material of following weight part:
Described initiator is selected from dibenzoyl peroxide;
Described dispersion agent is selected from sodium polymethacrylate;
Described emulsifying agent is selected from hydrogenated castor oil;
A preparation method for PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, comprises the following steps:
(1), by the industrial pure water of the high density polyethylene(HDPE) of 18-26 weight part, 500-600 weight part, the initiator of 0.075-0.1 weight part, the emulsifying agent of 0.15-0.25 weight part and the dispersant of 0.5-0.8 weight part drop into reactor, after 30-50 DEG C of emulsified 30-50min, heat up;
(2), logical chlorine;
(3), emptying after, cooling, discharging;
(4), after depickling, neutralization, make pH reach 7, then wash, after centrifugal, drying, obtain PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene.
Further, described in step (2), logical chlorine is specially:
A, below raw material HDPE fusing point even logical chlorine, chlorination is after 10 ~ 25% to product chlorinity, stops leading to chlorine;
B, be warming up to more than raw material HDPE melting point onset, heat preservation hot process;
C, be cooled to below raw material HDPE malcrystalline fusing point, evenly logical chlorine, react to product chlorinity be 36 ± 2%.
Further, in step a, 2-8 DEG C below raw material HDPE fusing point, evenly the logical chlorine time is 2h;
Further, in step b, be warming up to more than raw material HDPE melting point onset 2 DEG C, heat preservation hot process 40min.
Further, in step c, be cooled to below raw material HDPE malcrystalline fusing point 2-8 DEG C, evenly the logical chlorine time is 1.0h.
Further, emptyingly described in step (3) to be specially: at pressure≤0.2MPa, emptying when temperature is more than 100 DEG C;
Further, described in step (3), drop temperature is 60-80 DEG C.
Further, in step (4), in and time temperature control below 90 DEG C, in and time 2-3h;
Further, in step (4), neutralization reagent is Na
2cO
3, every 1kg high density polyethylene(HDPE) Na
2cO
350g.
The application of a kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene provided by the invention, as the application of PVG unitary-core flame-resistant conveying belt properties-correcting agent, can substitute paracril, the excellent performance of the PVG unitary-core flame-resistant conveying belt of preparation.
Chlorinatedpolyethylene (CPE) be polyethylene (PE) through chlorination modified product, it has excellent performance:
Because molecular chain has saturated structures, it has excellent weathering resistance, resistance to ozone, chemical-resistant resistance and ageing-resistant performance etc., and decompose more than 170 DEG C ,-30 DEG C still have flexibility, and embrittlement temperature is below-70 DEG C; Chlorinatedpolyethylene has the dual nature of plastics and rubber concurrently, not only low temperature resistant but also have higher heat decomposition temperature; Its molecular structure has polarity segment and nonpolar segment, and thus consistency is good, can with PVC, PE, PS and multiple blend rubber, improve their performance; The kindliness of its molecular chain makes it have good toughness at normal temperatures; Chlorinatedpolyethylene is nontoxic, processibility good, and wear resistant, stress cracking resistance are excellent; Polarity chlorine atom in molecule, makes it have good oil-proofness, flame retardant resistance and tint permanence; When CPE cl content is low, its performance is close to polyethylene, and during chlorinity height, performance, close to polyvinyl chloride, therefore, controls suitable chlorinity, can make it the advantage of both.Adopt different chloridization process, the product of rubber-like to rigid plastics shape can be obtained.Its maximum advantage all has good consistency with resins such as PVC, PS, ABS, MBS, PE, NR, EPDM, NBR, therefore, CPE both can as special synthetic rubber, again can as the properties-correcting agent of plastics or elastomeric material, along with the development of macromolecular material industry, the Application Areas of CPE is also being enriched constantly.
Current CPE aqueous suspension chlorination process, most employing three step leads to chlorine method, three sections are divided into PE melting temperature from kick off temperature (about 80 DEG C)---low-temperature zone, middle-temperature section and high temperature section, obtain the CPE product of different performance by the logical chlorine dose controlling this three temperature section; But three sections of chlorination process operations are more complicated, and logical chlorine dose and the influence factor of temperature section mode to CPE product performance of differing temps section are more complicated, are difficult to the product of production pre-determined characteristics;
And common two-stage method chloridization process, although simple to operate, the CPE product elasticity produced is poor, this is because two periods of chlorination process high temperature section reaction times are short, logical chlorine dose is few, can not in the abundant chlorination in PE crystallizing field, and CPE product is remaining, and crystallization is high causes.
Select three sections of traditional chlorination processs, because chlorination reaction is relatively more even, product residual crystallinity is little, thus give the elasticity of product fine, but its bad mechanical strength, wear resisting property is bad, also should not be used for flame-retardant conveyer belt coating rubber to substitute (or Some substitute) NBR.
Development research CPE product is with alternative paracril, and the product that need to change products have more excellent elasticity compared with common CP E and just can meet service requirements, and namely CPE need have higher elongation at break; And adopting the CPE of conventional three sections or two sections chloridization process productions, its performance can not meet the application requiring of PVG unitary-core flame-resistant conveying belt.
Compared with prior art, the present invention is to raise the low pressure polyethylene special raw material of sub-petrochemical iy produced for raw material, adopt the chloridization process of " two-stage method+thermal treatment ", first below raw material HDPE fusing point, chlorination is after 10 ~ 25% to chlorinity, stops leading to chlorine, is then warming up to more than HDPE melting point onset 2 DEG C, thermal treatment 40 minutes, less to ensure CPE residual crystallinity, improve the elasticity of CPE, CPE elastomer characteristic is highlighted.To be cooled to again near malcrystalline fusing point and introduce chlorine gas to make reaction to the cl content 36% of regulation, thus obtained there is good physical strength, there is again the CPE product of good caoutchouc elasticity.Product prepared by the present invention successfully replaces paracril 50%, the PVG unitary-core flame-resistant conveying belt excellent performance of preparation.
Accompanying drawing explanation
Fig. 1 is preparation technology's schematic flow sheet.
Embodiment
Embodiment 1
A kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, comprises the raw material of following weight part:
High density polyethylene(HDPE) is selected from the model YEC5515T raising sub-petrochemical iy produced, and fusing point is 134 DEG C.
A preparation method for PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, comprises the following steps:
(1), by the industrial pure water of 1.8kg high density polyethylene(HDPE), 50kg, 7.5g dibenzoyl peroxide, 15g hydrogenated castor oil and the mixing of 52g sodium polymethacrylate drop into reactor, after 30 DEG C of emulsified 40min, heat up;
(2), be heated to 128 DEG C, evenly logical chlorine, 2h chlorination is after 15% to product chlorinity, stops leading to chlorine; Be warming up to 136 DEG C, heat preservation hot process 40min; Be cooled to 128 DEG C, evenly logical chlorine 1h, react to product chlorinity be 36%;
(3), at 110 DEG C, emptying during pressure≤0.2MPa, be cooled to 60 DEG C of dischargings;
(4), through depickling, add 90g Na
2cO
3after neutralization, washing, makes pH reach 7, then washes away the alkali that CM particle surface contains, obtain PVC/HDPE increase-volume chlorinatedpolyethylene after centrifuge dehydration 6min, drying.
The application of a kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene provided by the invention, as the application of PVG unitary-core flame-resistant conveying belt properties-correcting agent.
Embodiment 2
A kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, comprises the raw material of following weight part:
High density polyethylene(HDPE) is selected from the model YEC5515T raising sub-petrochemical iy produced, and fusing point is 134 DEG C.
A preparation method for PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, comprises the following steps:
(1), by the industrial pure water of 2kg high density polyethylene(HDPE), 55kg, 8g dibenzoyl peroxide, 20g hydrogenated castor oil and the mixing of 60g sodium polymethacrylate drop into reactor, after 40 DEG C of emulsified 30min, heat up;
(2), be heated to 129 DEG C, evenly logical chlorine, 2h chlorination is after 18% to product chlorinity, stops leading to chlorine; Be warming up to 136 DEG C, heat preservation hot process 40min; Be cooled to 129 DEG C, evenly logical chlorine 1h, react to product chlorinity be 36%;
(3), at 110 DEG C, pressure≤0.2MPa time is emptying, is cooled to 70 DEG C of dischargings;
(4), through depickling, add 100g Na
2cO
3after neutralization, washing, makes pH reach 7, then washes away the alkali that CM particle surface contains, obtain PVC/HDPE increase-volume chlorinatedpolyethylene after centrifuge dehydration 6min, drying.
The application of a kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene provided by the invention, as the application of PVG unitary-core flame-resistant conveying belt properties-correcting agent.
Embodiment 3
A kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, comprises the raw material of following weight part:
High density polyethylene(HDPE) is selected from the model YEC5515T raising sub-petrochemical iy produced, and fusing point is 134 DEG C.
A preparation method for PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, comprises the following steps:
(1), by the industrial pure water of 2.6kg high density polyethylene(HDPE), 59kg, 9.8g dibenzoyl peroxide, 25g hydrogenated castor oil and the mixing of 76g sodium polymethacrylate drop into reactor, after 50 DEG C of emulsified 30min, heat up;
(2), be heated to 126 DEG C, evenly logical chlorine, 2h chlorination is after 20% to product chlorinity, stops leading to chlorine; Be warming up to 136 DEG C, heat preservation hot process 40min; Be cooled to 126 DEG C, evenly logical chlorine 1h, react to product chlorinity be 36%;
(3), at 105 DEG C, emptying during pressure≤0.2MPa, be cooled to 60 DEG C of dischargings;
(4), through depickling, add 130g Na
2cO
3after neutralization, washing, makes pH reach 7, then washes away the alkali that CM particle surface contains, obtain PVC/HDPE increase-volume chlorinatedpolyethylene after centrifuge dehydration 6min, drying.
The application of a kind of PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene provided by the invention, as the application of PVG unitary-core flame-resistant conveying belt properties-correcting agent.
The PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene performance ginseng that embodiment 1-3 prepares
Number is as following table 1:
Table 1
Application Example
The PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene prepared by embodiment 1-3 is applied in PVG unitary-core flame-resistant conveying belt, and its performance perameter is as following table 2:
Table 2
Illustrate:
1, in formula, except co-mixing system and vulcanization system, all the other compositions are constant.
2, blending technology condition and expressing technique condition constant.
3, These parameters all reaches the index request of flame-retardant conveyer belt coating rubber.
Claims (10)
1. a PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene, is characterized in that, described PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene comprises the raw material of following weight part:
2. PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene according to claim 1, it is characterized in that, described initiator is selected from dibenzoyl peroxide.
3. PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene according to claim 1 and 2, it is characterized in that, described dispersion agent is selected from sodium polymethacrylate.
4. the PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene according to any one of claim 1-3, it is characterized in that, described emulsifying agent is selected from hydrogenated castor oil.
5. a preparation method for the PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene described in any one of claim 1-4, it is characterized in that, described preparation method comprises the following steps:
(1), by the industrial pure water of the high density polyethylene(HDPE) of 18-26 weight part, 500-600 weight part, the initiator of 0.075-0.1 weight part, the emulsifying agent of 0.15-0.25 weight part and the dispersant of 0.5-0.8 weight part drop into reactor, after 30-50 DEG C of emulsified 30-50min, heat up;
(2), logical chlorine;
(3), emptying after, cooling, discharging;
(4), after depickling, neutralization, make pH reach 7, then wash, after centrifugal, drying, obtain PVG unitary-core flame-resistant conveying belt chlorinatedpolyethylene.
6. preparation method according to claim 5, is characterized in that, described in step (2), logical chlorine is specially:
A, below raw material HDPE fusing point even logical chlorine, chlorination is after 10 ~ 25% to product chlorinity, stops leading to chlorine;
B, be warming up to more than raw material HDPE melting point onset, heat preservation hot process;
C, be cooled to below raw material HDPE malcrystalline fusing point, evenly logical chlorine, react to product chlorinity be 36 ± 2%.
7. preparation method according to claim 5, is characterized in that, in step (4), neutralization reagent is Na
2cO
3, every 1kg high density polyethylene(HDPE) Na
2cO
350g.
8. preparation method according to claim 6, is characterized in that, in step a, 2-8 DEG C below raw material HDPE fusing point, evenly the logical chlorine time is 2h.
9. preparation method according to claim 6, is characterized in that, in step b, is warming up to more than raw material HDPE melting point onset 2 DEG C, heat preservation hot process 40min.
10. the preparation method according to any one of claim 6, is characterized in that, in step c, is cooled to below raw material HDPE malcrystalline fusing point 2-8 DEG C, and evenly the logical chlorine time is 1.0h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510487909.9A CN104987436A (en) | 2015-08-07 | 2015-08-07 | Chlorinated polyethylene for PVG whole core fire resistant belt, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510487909.9A CN104987436A (en) | 2015-08-07 | 2015-08-07 | Chlorinated polyethylene for PVG whole core fire resistant belt, preparation method and application thereof |
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|---|---|
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|---|---|---|---|
| CN201510487909.9A Pending CN104987436A (en) | 2015-08-07 | 2015-08-07 | Chlorinated polyethylene for PVG whole core fire resistant belt, preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3759888A (en) * | 1970-11-03 | 1973-09-18 | Osaka Soda Co Ltd | Ons thereof process for the preparation of chlorinated polyethylene and compositi |
| US4547554A (en) * | 1982-06-25 | 1985-10-15 | Osaka Soda Co., Ltd. | After-chlorinated ethylene/butene-1 copolymer and process for its production |
-
2015
- 2015-08-07 CN CN201510487909.9A patent/CN104987436A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3759888A (en) * | 1970-11-03 | 1973-09-18 | Osaka Soda Co Ltd | Ons thereof process for the preparation of chlorinated polyethylene and compositi |
| US4547554A (en) * | 1982-06-25 | 1985-10-15 | Osaka Soda Co., Ltd. | After-chlorinated ethylene/butene-1 copolymer and process for its production |
Non-Patent Citations (1)
| Title |
|---|
| 王从开: "大倾角橡胶花纹整芯阻燃输送带的研制", 《淮北职业技术学院学报》 * |
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Application publication date: 20151021 |
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