CN108250630A - A kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC and preparation method thereof - Google Patents
A kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC and preparation method thereof Download PDFInfo
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- CN108250630A CN108250630A CN201810135995.0A CN201810135995A CN108250630A CN 108250630 A CN108250630 A CN 108250630A CN 201810135995 A CN201810135995 A CN 201810135995A CN 108250630 A CN108250630 A CN 108250630A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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Abstract
The invention belongs to high molecular material application fields, are related to a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC and preparation method thereof, component and its parts by weight are：100 mass parts of PVC resin powder, 3~6 mass parts of stabilizer, 0.5~2 mass parts of lubricant, 1~3 mass parts of processing aid, 1~4 mass parts of foaming agent, 8~25 mass parts of filler, 3~6 mass parts of anti-flaming smoke-inhibiting agent.The present invention, using the phosphomolybdic acid copper being prepared under water bath condition as anti-flaming smoke-inhibiting agent, is added in the production of the hard foamed planks of PVC, simple for process, yield is high, and flame-retardant smoke inhibition is with obvious effects using phosphomolybdic acid and basic zinc carbonate as raw material with reference to other auxiliary agents.
Description
Technical field
The invention belongs to high molecular material application fields, are related to a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC
And preparation method thereof.
Background technology
PVC foam plate main chemical compositions are polyvinyl chloride (Polyvinyl chloride), so also referred to as foam gathers
Vinyl chloride sheet.It is widely used in each fields such as industry, agricultural, traffic, building, communication, health care, such as industrial spare and accessory parts,
Paulin, water pipe, plastic door-window, cable protective sleeve, medical product etc..Although hard PVC self flame retardances are had excellent performance, foaming
The decline of PVC material flame retardant property can be caused, and the amplitude of the smaller decline of density is bigger, particularly its forced burning in air
When can release a large amount of black smoke, and black smoke is factor most fatal in fire.Therefore the hard foamed plank to PVC is needed to hinder
Combustion suppression cigarette processing.
Invention content
To solve the above problems, the present invention provides a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC and its preparation
Method.
The present invention provides a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC, and component and its parts by weight are：PVC
100 mass parts of resin-oatmeal, 3~6 mass parts of stabilizer, 0.5~2 mass parts of lubricant, 1~3 mass parts of processing aid, foaming agent
1~4 mass parts, 8~25 mass parts of filler, 3~6 mass parts of anti-flaming smoke-inhibiting agent.
Specifically, the PVC resin powder is SG-7 resins.
Specifically, the stabilizer is Ca-Zn composite heat stabilizer.
Specifically, the foaming agent is sodium bicarbonate and azodicarbonamide.
Specifically, the lubricant is polyethylene wax and stearic acid.
Specifically, the processing aid is acrylate copolymer.
Specifically, the filler is 1250 mesh calcium carbonate.
Specifically, the anti-flaming smoke-inhibiting agent is phosphomolybdic acid copper, it is raw material by phosphomolybdic acid and basic zinc carbonate, using water-bath
Under the conditions of be prepared.
The present invention provides the preparation method of the hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC described in any one of the above embodiments,
Include the following steps：
1) PVC resin powder and auxiliary agent are added in into the mixed pot of heat and stirred, after temperature reaches 100~130 DEG C, stirring 2~5
Minute, be then put into cold mixing pot and stir cooling, 40~60 DEG C or so whens, discharge, material it is cold it is mixed after screened machine enter it is dry
Blending bunker is stored；
2) dry blend is sent to extrusion line when using, extruded machine screw zones temperature is：I 150 DEG C of area, 165 DEG C of IIth area,
III 170 DEG C of area, 170 DEG C of IVth area make foaming agent decompose release bubble and incorporate in melt；
3) after melt extrusion mold, shaping cover cooling and shaping is immediately entered, is further cooled down into water tank, by dragger
After be cut into finished product.
The smoke-suppression mechanism of the present invention is：Phosphomolybdic acid copper (Cu3[PMo12O40]2) in heating process, it is thermally decomposed
Into copper compound, PVC combustion processes is promoted to decompose generation allylic chlorine radicals, crosslinking is generated, reduces conjugated polyene chain and formed,
Intramolecular cyclization reaction is caused to be suppressed, the production quantity of benzene reduces when in turn resulting in PVC degradations, so as to play the suppression cigarette to PVC
Effect.At the same time, reductive coupling reaction also eliminates the decomposition of allylic chlorine radicals, it is suppressed that " zip mode " is chain de-
HCl reacts, and slows down the thermal decomposition of PVC, improves the thermal stability of PVC, play fire retardation.
PVC resin powder SG-7 resins, are matrixes；Stabilizer is Ca-Zn composite heat stabilizer, and it is steady to improve PVC process
It is qualitative, and be stabilizer；Processing aid is acrylate copolymer, and abbreviation ACR promotes polyvinyl chloride resin plasticizing；Foaming agent
For sodium bicarbonate and azodicarbonamide；Lubricant is polyethylene wax and stearic acid, and polyethylene wax is external lubricant, and stearic acid is
In-lubricant；Filler is 1250 mesh precipitated calcium carbonates, promotes PVC plastic, improves its toughness and tensile strength.
The beneficial effects of the present invention are：It is raw material by phosphomolybdic acid and basic zinc carbonate, using preparing PVC under water bath condition
The anti-flaming smoke-inhibiting agent phosphomolybdic acid copper (Cu of hard foamed plank3[PMo12O40]2).Phosphomolybdic acid copper anti-flaming smoke-inhibiting agent can improve PVC
The oxygen index (OI) of hard foamed plank inhibits the smoke amount of the hard foamed planks of PVC, and with obvious effects.Add anti-flaming smoke-inhibiting agent phosphorus
The hard foamed planks of PVC of copper molybdate have the features such as simple production process, yield is high, and product flame-retardant smoke inhibition is with obvious effects.
Specific embodiment
Technical scheme of the present invention is described further below, however, it is not limited to this, all using to the technology of the present invention
Scheme is replaced on an equal basis or modification, without departing from the technology of the present invention principle and purport, should all cover the present invention claims protection model
It encloses.
Embodiment 1
Each component is weighed according to parts by weight, respectively 100 mass parts of SG-7 resins, 3 mass of Ca-Zn composite heat stabilizer
Part, 0.3 mass parts of polyethylene wax, 0.2 mass parts of stearic acid, processing aid ACR2 mass parts, 1.2 mass parts of sodium bicarbonate, idol
0.5 mass parts of nitrogen diformamide, 1250 mesh calcium carbonate, 11 mass parts, 4 mass parts of phosphomolybdic acid copper.
Embodiment 2
Each component is weighed according to parts by weight, respectively 100 mass parts of SG-7 resins, 5 mass of Ca-Zn composite heat stabilizer
Part, 0.4 mass parts of polyethylene wax, 0.5 mass parts of stearic acid, processing aid ACR3 mass parts, 1.6 mass parts of sodium bicarbonate, idol
0.6 mass parts of nitrogen diformamide, 1250 mesh calcium carbonate, 8 mass parts, 5 mass parts of phosphomolybdic acid copper.
Embodiment 3
Each component is weighed according to parts by weight, respectively 100 mass parts of SG-7 resins, 6 mass of Ca-Zn composite heat stabilizer
Part, 0.3 mass parts of polyethylene wax, 0.5 mass parts of stearic acid, processing aid ACR2 mass parts, 1.3 mass parts of sodium bicarbonate, idol
0.4 mass parts of nitrogen diformamide, 1250 mesh calcium carbonate, 25 mass parts, 6 mass parts of phosphomolybdic acid copper.
Embodiment 4
Each component is weighed according to parts by weight, respectively 100 mass parts of SG-7 resins, 4 mass of Ca-Zn composite heat stabilizer
Part, 0.5 mass parts of polyethylene wax, 0.7 mass parts of stearic acid, processing aid ACR1 mass parts, 0.9 mass parts of sodium bicarbonate, idol
0.3 mass parts of nitrogen diformamide, 1250 mesh calcium carbonate, 15 mass parts, 3 mass parts of phosphomolybdic acid copper.
Embodiment 5
Each component is weighed according to parts by weight, respectively 100 mass parts of SG-7 resins, 4 mass of Ca-Zn composite heat stabilizer
Part, 0.3 mass parts of polyethylene wax, 0.2 mass parts of stearic acid, processing aid ACR1.5 mass parts, 0.7 mass parts of sodium bicarbonate,
0.3 mass parts of azodicarbonamide, 1250 mesh calcium carbonate, 16 mass parts, 5 mass parts of phosphomolybdic acid copper.
Comparative example
Each component is weighed according to parts by weight, respectively 100 mass parts of SG-7 resins, 4 mass of Ca-Zn composite heat stabilizer
Part, 0.3 mass parts of polyethylene wax, 0.2 mass parts of stearic acid, processing aid ACR2 mass parts, 1.2 mass parts of sodium bicarbonate, idol
0.5 mass parts of nitrogen diformamide, 1250 mesh calcium carbonate, 11 mass parts, 5 parts of anti-flaming smoke-inhibiting agent.Use molybdenum trioxide and ammonium octamolybdate
In mass ratio 3:2 are used as composite flame-proof smoke suppressant.
Blank sample
Each component is weighed according to parts by weight, respectively 100 mass parts of SG-7 resins, 4 mass of Ca-Zn composite heat stabilizer
Part, 0.3 mass parts of polyethylene wax, 0.2 mass parts of stearic acid, processing aid ACR2 mass parts, 1.2 mass parts of sodium bicarbonate, idol
0.5 mass parts of nitrogen diformamide, 1250 mesh calcium carbonate, 11 mass parts.
Examples 1 to 5, blank sample and comparative example are prepared according to below step：
1) it is put into the mixed pot of heat and stirs after weighing polyvinyl chloride resin and various auxiliary materials, when temperature reaches 100~130 DEG C or so
When, stir 2~5 minutes, be then put into cold mixing pot and stir cooling, 40~60 DEG C or so whens, discharge, material it is cold it is mixed finish after pass through
Screening machine is stored into dry-mixed feed bin；
2) dry blend is sent to from dry-mixed feed bin in each extrusion line by stirring cage and chain conveyor when using, it is powdered
Material after the hopper in extrusion line enters extruder, with continuous Forward, slowly from solid state transformed for viscous state, foaming
Agent also begins to decompose, but due to extruder and mold special construction so that the melt pressure in machine barrel and mold is very high, foaming
The gas that agent decomposes to give off is dissolved at elevated pressures among PVC melts, wherein squeezing out the temperature setting in each area of unit：I area 150
DEG C, 165 DEG C of IIth area, 170 DEG C of IIIth area, 170 DEG C of IVth area, die lip temperature is 80 DEG C, tube calibration device temperature is 25 DEG C；
3) after melt is extruded mold, since melt loses pressure suddenly, the bubble dissolved in the melt expands rapidly
Foaming, at this moment immediately enters shaping cover cooling and shaping, then enters back into water tank and further cool down, cut as required after dragger
It is segmented into the finished product of certain length.
The above-mentioned plank being prepared is tested for the property, the results are shown in Table 1.
1 flame retarding and smoke suppressing properties test result of table
| Oxygen index (OI) % | Smoke density MSD | Smoke density grade SDR | |
| Blank sample | 31.55 | 91.58 | 78.33 |
| Embodiment 1 | 36.26 | 73.74 | 60.06 |
| Embodiment 2 | 39.37 | 65.17 | 49.75 |
| Embodiment 3 | 42.94 | 62.55 | 48.26 |
| Embodiment 4 | 35.65 | 74.64 | 60.61 |
| Embodiment 5 | 40.28 | 70.55 | 49.67 |
| Comparative example | 36.68 | 74.36 | 62.63 |
Above-described embodiment and blank sample and comparative example relatively find out that the application of phosphomolybdic acid copper is than molybdenum trioxide and eight molybdenums
Sour ammonium in mass ratio 3:2 as composite flame-proof smoke suppressant oxygen index (OI) is larger, smoke density is smaller, and phosphomolybdic acid copper mass part higher
Embodiment 2,3 and 5 smoke density effect it is more preferable.
Claims (9)
1. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC, which is characterized in that its component and its parts by weight are：PVC trees
100 mass parts of cosmetics, 3~6 mass parts of stabilizer, 0.5~2 mass parts of lubricant, 1~3 mass parts of processing aid, foaming agent 1
~4 mass parts, 8~25 mass parts of filler, 3~6 mass parts of anti-flaming smoke-inhibiting agent.
2. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC according to claim 1, it is characterised in that：It is described
PVC resin powder be SG-7 resins.
3. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC according to claim 1, it is characterised in that：It is described
Stabilizer be Ca-Zn composite heat stabilizer.
4. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC according to claim 1, it is characterised in that：It is described
Foaming agent be sodium bicarbonate and azodicarbonamide.
5. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC according to claim 1, it is characterised in that：It is described
Lubricant be polyethylene wax and stearic acid.
6. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC according to claim 1, it is characterised in that：It is described
Processing aid is acrylate copolymer.
7. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC according to claim 1, it is characterised in that：It is described
Filler be 1250 mesh calcium carbonate.
8. a kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC according to claim 1, it is characterised in that：It is described
Anti-flaming smoke-inhibiting agent for phosphomolybdic acid copper, be raw material by phosphomolybdic acid and basic zinc carbonate, using being prepared under water bath condition.
9. according to the preparation method of the hard foamed plank of claim 1~8 any one of them phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC,
It is characterized in that：Include the following steps：
1) PVC resin powder and auxiliary agent are added in into the mixed pot of heat and stirred, after temperature reaches 100~130 DEG C, stir 2~5 points
Then clock is put into cold mixing pot and stirs cooling, 40~60 DEG C or so whens discharge, material it is cold it is mixed after screened machine enter it is dry-mixed
Feed bin is stored；
2) dry blend is sent to extrusion line when using, extruded machine screw zones temperature is：I 150 DEG C of area, 165 DEG C of IIth area, IIIth area
170 DEG C, 170 DEG C of IVth area make foaming agent decompose release bubble and incorporate in melt；
3) after melt extrusion mold, shaping cover cooling and shaping is immediately entered, further cools down into water tank, is cut after dragger
It is segmented into finished product.
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| CN201810135995.0A CN108250630A (en) | 2018-02-09 | 2018-02-09 | A kind of hard foamed plank of phosphomolybdic acid copper fire-resistant smoke-inhibiting PVC and preparation method thereof |
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| CN109021456A (en) * | 2018-08-22 | 2018-12-18 | 宝天高科（广东）有限公司 | A kind of flame-retardant smoke inhibition environment-friendly PVC low ratio foamed plate and preparation method thereof |
| CN111471256A (en) * | 2020-06-11 | 2020-07-31 | 安徽奥凯材料股份有限公司 | Copper phosphotungstate smoke suppression PVC (polyvinyl chloride) hard board and preparation method thereof |
| CN113600203A (en) * | 2021-07-28 | 2021-11-05 | 新疆至臻化工工程研究中心有限公司 | Copper molybdate catalyst for synthesizing chloroethylene and preparation method thereof |
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| CN109021456A (en) * | 2018-08-22 | 2018-12-18 | 宝天高科（广东）有限公司 | A kind of flame-retardant smoke inhibition environment-friendly PVC low ratio foamed plate and preparation method thereof |
| CN111471256A (en) * | 2020-06-11 | 2020-07-31 | 安徽奥凯材料股份有限公司 | Copper phosphotungstate smoke suppression PVC (polyvinyl chloride) hard board and preparation method thereof |
| CN113600203A (en) * | 2021-07-28 | 2021-11-05 | 新疆至臻化工工程研究中心有限公司 | Copper molybdate catalyst for synthesizing chloroethylene and preparation method thereof |
| CN113600203B (en) * | 2021-07-28 | 2024-01-12 | 新疆至臻化工工程研究中心有限公司 | Copper molybdate catalyst for synthesizing chloroethylene and preparation method thereof |
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