CN1250640C - PVC flame retarding smoke inhibitor, PVC therefrom and preparing method thereof - Google Patents
PVC flame retarding smoke inhibitor, PVC therefrom and preparing method thereof Download PDFInfo
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- CN1250640C CN1250640C CN 200410022771 CN200410022771A CN1250640C CN 1250640 C CN1250640 C CN 1250640C CN 200410022771 CN200410022771 CN 200410022771 CN 200410022771 A CN200410022771 A CN 200410022771A CN 1250640 C CN1250640 C CN 1250640C
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Abstract
The present invention discloses a new PVC flame-retardant smoke inhibiting agent, flame-retardant smoke inhibiting PVC using the flame-retardant smoke inhibiting agent as a main component and a preparation method thereof. The PVC flame-retardant smoke inhibiting agent is mainly composed of molybdenum oxide (MoO3), antimony trioxide (Sb2O3), zinc borate (ZB) and interface reinforcing agents, and the flame-retardant smoke inhibiting PVC is mainly composed of PVC resin, flame-retardant smoke inhibiting agents, stabilizing agents and lubricants. The preparation method for the flame-retardant smoke inhibiting agent comprises the steps that the dried molybdenum oxide (MoO3), the dried antimony trioxide (Sb2O3), the dried zinc borate (ZB) and the dried interface reinforcing agents are compounded according to a certain proportion, and after all the components are processed by force chemical vibration milling, the new flame-retardant smoke inhibiting agent is prepared. The flame-retardant smoke inhibiting agent is added in the PVC resin, and a PVC product is obtained; the flame-retardant smoke inhibiting properties of the PVC product are greatly enhanced, and simultaneously, the mechanical properties are improved. The flame-retardant smoke inhibiting agent can be widely used in various products, such as polyvinyl chloride pipe materials, profiled bars, plates, corrugated pipes, etc.
Description
One, technical field
The present invention relates to technical field of polymer, more particularly relate to be used for the anti-flaming smoke-inhibiting agent of polyvinyl chloride (PVC) and contain the PVC of anti-flaming smoke-inhibiting agent, and about the preparation method of anti-flaming smoke-inhibiting agent.
Two, background technology
Polyvinyl chloride (PVC) is second largest general-purpose plastics, and it is widely used in every field with its good ratio of performance to price.Along with to mould Dai Gang, with the development and the popularization of moulding Dai Mu, PVC is able to fast development especially as chemical building material in recent years.But PVC can generate a large amount of harmful smog when burning, so the flame-retardant smoke inhibition problem of PVC material becomes a research focus in PVC field.Anti-flaming smoke-inhibiting agent (FRs) at present both at home and abroad commonly used mainly contains following a few class: 1) halogen containing flame-retardant, 2) phosphorus-nitrogen flame retardant, 3) the nitrogen based flameproofing, 4) hibbsite, magnesium hydroxide, 5) red phosphorus of micro encapsulation, 6) metal oxide etc.Above-mentioned these anti-flaming smoke-inhibiting agent ubiquity flame-retardant smoke inhibition efficient are not high; when improving its flame-retardant smoke inhibition performance; regular meeting reduces the mechanical property of goods etc. significantly, thereby has influence on problem such as its use properties, and therefore the development of new and effective anti-flaming smoke-inhibiting agent causes people's extensive attention.Yet traditional preparation method is big to synthetic new anti-flaming smoke-inhibiting agent kind difficulty.Thereby, explore new working method, novel with the research preparation, can improve the flame-retardant smoke inhibition performance of PVC effectively, can further improve mechanical property again, PVC anti-flaming smoke-inhibiting agent that reduces production costs and PVC prepared therefrom have important significance for theories and practical value.
Three, summary of the invention
A kind of novel PVC anti-flaming smoke-inhibiting agent that The present invention be directed to the deficiencies in the prior art and propose, by its fire-resistant smoke-inhibiting PVC that is prepared into and preparation method thereof, not high with the flame-retardant smoke inhibition efficient that solves anti-flaming smoke-inhibiting agent in the prior art, with problems such as the mechanical property of the PVC goods of its preparation can reduce significantly.
The concrete technical scheme that realizes above-mentioned purpose of the present invention is as follows:
The anti-flaming smoke-inhibiting agent that is used for polyvinyl chloride (PVC), its composition component mainly contains molybdic oxide (MoO
3), antimonous oxide (Sb
2O
3), coupling agent and polyvinyl chloride (PVC) resin, the weight part of each component (phr) is:
Molybdic oxide (MoO
3) 1.0～90phr
Antimonous oxide (Sb
2O
3) 1.0～90phr
Coupling agent 0.5～5.0phr
Polyvinyl chloride (PVC) resin 1.0～30phr.
Above-mentioned said PVC anti-flaming smoke-inhibiting agent, it forms the zinc borate (ZB) that component can also contain 0～80phr, and promptly zinc borate is inessential component.
Above-mentioned said coupling agent is actually a kind of interface toughener, can select in titanate coupling agent (NDZ), silane coupling agent (KH) and the aluminate coupling agent (DL) any for use.
With the fire-resistant smoke-inhibiting PVC that PVC anti-flaming smoke-inhibiting agent disclosed by the invention is prepared into, it forms component mainly by polyvinyl chloride resin, the PVC anti-flaming smoke-inhibiting agent, and thermo-stabilizer and lubricant are formed, and the weight part of each component is:
Polyvinyl chloride resin 100phr
Anti-flaming smoke-inhibiting agent 2.0～10phr
Thermo-stabilizer 2.0～6.0phr
Lubricant 0.2～1.0phr
Above-mentioned said thermo-stabilizer is selected organotin, lead sulfate tribasic, lead stearate and Ca-Zn one package stabilizer for use, can select wherein a kind of for use, also can select wherein at least two kinds for use.
Above-mentioned said lubricant is selected stearic acid, montanate, polyethylene sodium for use, can select wherein a kind of for use, also can select wherein at least two kinds for use.
The preparation method of above-mentioned said PVC anti-flaming smoke-inhibiting agent is the molybdenum oxide (MoO after drying is handled
3), antimonous oxide (Sb
2O
3), zinc borate (ZB) and coupling agent agent be by carrying out composite for certainty ratio under 10 ℃～40 ℃, again compound is mixed with the polyvinyl chloride resin powder of giving certainty ratio, afterwards mixture is inserted vibration 1～24 hour (h) in the vibration equipment, make the surperficial radical that forms with PVC of active particle that anti-flaming smoke-inhibiting agent composition component produces in the vibration process carry out abundant coupled reaction, make the PVC anti-flaming smoke-inhibiting agent.The high energy vibration that vibration can adopt per minute 100～1000 to change, service temperature is 10 ℃～40 ℃.Energy during vibration is high more, and the time of vibration is short more, otherwise the time of vibration is long more.The vibration time is so that the radical that active particle in anti-flaming smoke-inhibiting agent surface and PVC form is fully reacted is as the criterion.
Experimental result shows, adds novel flame-retardant provided by the invention and presses down the PVC that fumicants makes, and with respect to prior art, not only the flame-retardant smoke inhibition performance is greatly improved, and mechanical property is also effectively improved.It is as follows that its flame-retardant smoke inhibition performance increases substantially the reason of effectively being improved with mechanical property:
1. because different classes of anti-flaming smoke-inhibiting agent is different with mechanism to the mechanism of PVC, when being used, its effect obviously exists " the collaborative enhancing " and " cancelling out each other " two kinds of possibilities.The present invention has selected to have several anti-flaming smoke-inhibiting agent components of " the collaborative enhancing " effect, by composite in proportion, handle through the vibration of power chemistry, reached ideal flame-retardant smoke inhibition effect, add this anti-flaming smoke-inhibiting agent simultaneously in the PVC goods, the mechanical property of goods is well improved.
2. owing to adopted power chemistry vibration technology, in power chemistry vibration process, reduced the size of particles of anti-flaming smoke-inhibiting agent performance component effectively, increase its specific surface area, promote to form chemical bonding between itself and the PVC, improve the dispersive ability of FRs in base material, increase the interfacial interaction of FRs and PVC, effectively suppress the generation of PVC aromatic hydroxy compound in combustion processes, thereby improve the flame-retardant smoke inhibition efficient of PVC/FRs system, the mechanical property of improvement system makes the resistance to impact shock of system, and tensile strength and elongation at break are all significantly improved.Power chemistry vibration technology also can be used for improving the consistency and the dispersiveness of polymer blending infill system, prepares other difficult fabricated product.
Four, specifically implement formula
Below be the present invention to be specifically described by embodiment.In following each embodiment, the umber of each component is parts by weight (phr).
But form with tabulation provides 10 novel flame-retardants fumicants embodiment below
| Embodiment | Component | ||||
| MoO 3 | Sb 2O 3 | ZB | The interface toughener | Polyvinyl chloride resin | |
| I | 3 | 8 | 0.5 | NDZ-201：0.2 | 0.3 |
| II | 10 | 5 | 7 | NDZ-201：0.5 | 1.0 |
| III | 1 | 2.5 | 10 | NDZ-201：0.4 | 0.5 |
| IV | 7 | 3 | 1 | NDZ-201：0.3 | 1.0 |
| V | 1 | 90 | 5 | NDZ-201：4.0 | 10.0 |
| VI | 90 | 1 | 7 | KH-550：2.0 | 42.0 |
| VII | 1 | 1 | 80 | KH-560：1.0 | 1.5 |
| VIII | 7 | 8 | 0 | KH-570：0.5 | 5.0 |
| IX | 3 | 5 | 10 | DL-881：0.5 | 2.0 |
| X | 9 | 5 | 5 | DL-831：0.5 | 1.0 |
The preparation method that the PVC novel flame-retardant presses down fumicants is as follows:
The preparation of the anti-flaming smoke-inhibiting agent of embodiment 1 is under 25 ℃, with MoO after drying
3, Sb
2O
3, ZB and titanate coupling agent (NDZ-201) mix respectively in proportion, makes compound.Compound is mixed with the polyvinyl chloride resin powder of giving certainty ratio.Compound is placed vibration mill (500 rev/mins of rotating speeds), and under 25 ℃, resonance mill 12h promptly makes novel flame-retardant and presses down fumicants.
The preparation method of other embodiment is basic identical with the preparation method of embodiment 1.
Provide below with anti-flaming smoke-inhibiting agent provided by the invention is the embodiment and the test result of the novel flame-retardant smoke-inhibiting PVC of main ingredient
Embodiment 1:
Respectively with 2 parts anti-flaming smoke-inhibiting agent I, II, III, 3 parts of organo-tin het stabilizers, 0.2 part of stearic acid adds polyvinyl chloride resin (PVC-SG5, Mn=6.25 * 10
4, former chemical plant, sky, Yibin) in, in two roller roller refining equipment,, under 180 ℃, be molded into the sheet material and the sheet material of desired thickness again in 170 ℃ of roller refining 10min, be made for limiting oxygen index(LOI) (LOI), smoke density (Dm) and Mechanics Performance Testing and use.
Test result:
| Form | The contrast sample | Embodiment 1 | ||
| A | B | C | ||
| Polyvinyl chloride resin organo-tin het stabilizer stearic acid I II III The performance test results: limited oxygen index (LOI) smoke density (Dm) notched Izod impact strength (kJ/m2) tensile strength (MPa) elongation at break (%) | 100 3 0.2 - 47.0 85 2.96 62.38 151.5 | 100 3 0.2 2 64.0 75 5.93 64.17 80.6 | 100 3 0.2 2 69.6 71 6.27 65.18 94.0 | 100 3 0.2 2 77.3 69 5.93 64.6 152.7 |
Embodiment 2:
Respectively with 5 parts anti-flaming smoke-inhibiting agent I, II, II, 4 parts of lead sulfate tribasics, 1 part of lead stearate, 0.5 part of stearic acid adds polyvinyl chloride resin (PVC-SG5, Mn=6.25 * 10
4, former chemical plant, sky, Yibin) in, in two roller roller refining equipment,, under 180 ℃, be molded into the sheet material and the sheet material of desired thickness again in 170 ℃ of roller refining 10min, be made for LOI, Dm and Mechanics Performance Testing and use.
Test result:
| Form | The contrast sample | Embodiment 2 | ||
| A | B | C | ||
| Polyvinyl chloride resin lead sulfate tribasic lead stearate stearic acid I II III The performance test results: limited oxygen index (LOI) smoke density (Dm) notched Izod impact strength (kJ/m2) tensile strength (MPa) elongation at break (%) | 100 4 1 0.5 - 47.0 85 2.96 62.38 151.5 | 100 4 1 0.5 5 65.0 69 5.18 60.10 94.5 | 100 4 1 0.5 5 71.4 63 5.79 63.00 172.1 | 100 4 1 0.5 5 79.2 51 5.79 61.80 168.5 |
Embodiment 3:
Respectively with 10 parts anti-flaming smoke-inhibiting agent I, II, III, 3 parts of complex Ca-Zn thermo-stabilizers, 1.0 parts of montanates add polyvinyl chloride resin (PVC-SG5, Mn=6.25 * 10
4, former chemical plant, sky, Yibin) in, in two roller roller refining equipment,, under 180 ℃, be molded into the sheet material and the sheet material of desired thickness again in 170 ℃ of roller refining 10min, be made for LOI, Dm and Mechanics Performance Testing and use.
Test result:
| Form | The contrast sample | Embodiment 3 | ||
| A | B | C | ||
| Polyvinyl chloride resin Ca-Zn heat stabilizer montanate I II III The performance test results: limited oxygen index (LOI) smoke density (Dm) notched Izod impact strength (kJ/m2) tensile strength (MPa) elongation at break (%) | 100 2.5 1.0 - 47.0 85 2.96 62.38 151.5 | 100 2.5 1.0 10 65.2 59 5.83 58.15 91.9 | 100 2.5 1.0 10 76.1 52 6.31 63.19 199.5 | 100 2.5 1.0 10 80.0 49 6.45 62.57 154.7 |
Be necessary to be pointed out that at this above embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Claims (8)
1. a Polyvinyl Chloride Fire-Retardant Restrain Smoking Agent is characterized in that forming component and mainly contains molybdic oxide, antimonous oxide, coupling agent and polyvinyl chloride (PVC) RESINS, and the weight part of each component is:
Molybdic oxide 1.0～90phr
Antimonous oxide 1.0～90phr
Coupling agent 0.5～5.0phr
Polyvinyl chloride (PVC) RESINS 1.0～30phr.
2. according to claim 1 described Polyvinyl Chloride Fire-Retardant Restrain Smoking Agent, it is characterized in that forming the zinc borate that component also contains 0～80phr.
3. according to claim 1 or 2 described Polyvinyl Chloride Fire-Retardant Restrain Smoking Agents, it is characterized in that said coupling agent selects titanate coupling agent, silane coupling agent and aluminate coupling agent for use.
4. the flame-proof smoke-restraining polyvinyl chloride that contains the determined Polyvinyl Chloride Fire-Retardant Restrain Smoking Agent of each claim described in the claim 1 to 3, it is characterized in that forming component mainly by polyvinyl chloride (PVC) RESINS, Polyvinyl Chloride Fire-Retardant Restrain Smoking Agent, thermo-stabilizer and lubricant are formed, and the parts by weight of each component are:
Polyvinyl chloride (PVC) RESINS 100phr
Anti-flaming smoke-inhibiting agent 2.0～10phr
Thermo-stabilizer 2.0～6.0phr
Lubricant 0.2～1.0phr.
5. according to claim 4 described flame-proof smoke-restraining polyvinyl chlorides, it is characterized in that thermo-stabilizer selects organotin, lead sulfate tribasic, lead stearate and Ca-Zn one package stabilizer for use.
6. according to claim 4 described flame-proof smoke-restraining polyvinyl chlorides, it is characterized in that lubricant selects stearic acid, montanate, Ployethylene Wax for use.
7. be used to prepare the method for the Polyvinyl Chloride Fire-Retardant Restrain Smoking Agent described in the claim 1 to 3, it is characterized in that molybdic oxide, antimonous oxide, zinc borate and coupling agent after the drying processing by under 10 ℃～40 ℃, carrying out composite for certainty ratio, again compound is mixed with the polyvinyl chloride resin powder of giving certainty ratio, afterwards mixture was inserted in the vibration equipment vibration 1～24 hour, make active particle surface that anti-flaming smoke-inhibiting agent produces in the vibration process and the radical that polyvinyl chloride forms carry out abundant coupled reaction, make the PVC anti-flaming smoke-inhibiting agent.
8. according to the preparation method of claim 7 described Polyvinyl Chloride Fire-Retardant Restrain Smoking Agents, it is characterized in that said vibration is 100～1000 rev/mins high energy vibration, service temperature is 10 ℃～40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410022771 CN1250640C (en) | 2004-06-11 | 2004-06-11 | PVC flame retarding smoke inhibitor, PVC therefrom and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410022771 CN1250640C (en) | 2004-06-11 | 2004-06-11 | PVC flame retarding smoke inhibitor, PVC therefrom and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583869A CN1583869A (en) | 2005-02-23 |
| CN1250640C true CN1250640C (en) | 2006-04-12 |
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ID=34600719
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410022771 Expired - Fee Related CN1250640C (en) | 2004-06-11 | 2004-06-11 | PVC flame retarding smoke inhibitor, PVC therefrom and preparing method thereof |
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|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554768A (en) * | 2013-10-30 | 2014-02-05 | 安徽国通高新管业股份有限公司 | Flame-retardant corrugated pipe |
| CN108892890A (en) * | 2018-06-07 | 2018-11-27 | 天津科技大学 | Fire resisting presses down cigarette hard PVC plate |
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2004
- 2004-06-11 CN CN 200410022771 patent/CN1250640C/en not_active Expired - Fee Related
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|---|---|
| CN1583869A (en) | 2005-02-23 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Ningbo Alishan Adhesive Products Co., Ltd. Assignor: Sichuan University Contract fulfillment period: 2008.9.16 to 2023.9.15 contract change Contract record no.: 2008330001370 Denomination of invention: PVC flame retarding smoke inhibitor, PVC therefrom and preparing method thereof Granted publication date: 20060412 License type: Exclusive license Record date: 20081027 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.9.16 TO 2023.9.15; CHANGE OF CONTRACT Name of requester: NINGBO ALISHAN GLUING PRODUCTS SCIENCE CO., LTD. Effective date: 20081027 |
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