CN103232654A - Composite flame retardant capable of improving flame retardant property of PVC and application thereof - Google Patents
Composite flame retardant capable of improving flame retardant property of PVC and application thereof Download PDFInfo
- Publication number
- CN103232654A CN103232654A CN201310183033XA CN201310183033A CN103232654A CN 103232654 A CN103232654 A CN 103232654A CN 201310183033X A CN201310183033X A CN 201310183033XA CN 201310183033 A CN201310183033 A CN 201310183033A CN 103232654 A CN103232654 A CN 103232654A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- composite flame
- retardant
- agent
- pvc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention provides a composite flame retardant which is formed by mixing ZnSiO3 with Mg(OH)2 in a mixing ratio of 1:9. The composite flame retardant is added to soft PVC (polyvinyl chloride) resins; and a series of tests on mechanical properties and combustion performance and the exploration of the flame-retardant mechanism are performed. Results indicate that when the dosage of the composite flame retardant is 20 parts, the influence on the physical and mechanical properties of the PVC is very small; due to synergistic flame retardant effect of ZnSiO3 with Mg(OH)2, the oxygen index of the sample may reach 31.8, the flame retardant performance of the sample is excellent and is up to the standard of the state specified nonflammable material; and the problem of contradiction between the mechanical properties and the flame retardant performance of the PVC caused by addition of lots of Mg(OH)2 is solved. Besides, the composite flame retardant is low in toxicity; and due to compound utilization, the production cost is reduced.
Description
Technical field
The present invention relates to a kind of composite flame-retardant agent, be specifically related to a kind of composite flame-retardant agent for the PVC material.
Background technology
PVC (polyvinyl chloride) resin itself just has high flame retardant, and pure polyvinyl chloride resin oxygen index reaches 24.5, can think a kind of flame retardant properties excellent material.But often add a large amount of auxiliary agent (as softening agent, coupling agent etc.) in order to improving Drawing abillity and pliability in its course of processing, and auxiliary agent is generally inflammable substance, heavy addition can reduce the flame retardant resistance of flexible PVC greatly; In addition, it is big that PVC when burning given birth to the cigarette amount, and what add is organic based flame retardant mostly, not only poisonous, and cause secondary pollution easily.And inorganic combustion inhibitor is nontoxic or can prevent drip when low toxicity, burning, do not produce smog, a lot of effects that suppress smog in addition meet current fire retardant fully to the megatrend of environment-friendly type development, but a large amount of uses of China is the fire retardant of single variety, expensive, production cost is too high.Therefore, when improving the polyvinyl chloride resin flame retardant resistance, reducing the cost of fire retardant, is the main direction of studying at present.
How research makes it reasonably combined with the compound use of various inorganic combustion inhibitors, produces the effect that a kind of cooperative flame retardant eliminates smoke, significant.
Summary of the invention
The objective of the invention is to solve above-mentioned the deficiencies in the prior art, a kind of composite flame-retardant agent that can improve the PVC flame retardant properties is provided, the present invention passes through ZnSiO
3And Mg (OH)
2Compositely find a kind of new compound prescription, under to the little situation of polyvinyl chloride resin mechanical property influence, improve the flame retardant properties of polyvinyl chloride resin, in the hope of reducing its cost, be conducive to industrial production.
For achieving the above object, the present invention by the following technical solutions.
A kind of composite flame-retardant agent that can improve the PVC flame retardant properties is by ZnSiO
3With Mg (OH)
2Form, and ZnSiO
3: Mg (OH)
2Mass ratio be 1: 9.
The preparation method of described composite flame-retardant agent is: with ZnSiO
3With Mg (OH)
2Press mass ratio and mix at 1: 9, through fully grinding, after mixing, place moisture eliminator standby.
The invention also discloses the application method of described composite flame-retardant agent, concrete operations are as follows:
After polyvinyl chloride resin, softening agent, stablizer, coupling agent, lubricant and described composite flame-retardant agent mixed,, extrude at 140 ℃-160 ℃ mixing 15min down with twin screw extruder.
Preferable, more than each material consumption score by weight and be not: 100 parts of polyvinyl chloride resins, 40 parts in softening agent, 1 part of stablizer, 1 part of coupling agent, 1 part of lubricant and described composite flame-retardant agent 10-25 part.
Preferable, described softening agent is dioctyl phthalate (DOP).
Preferable, described stablizer is organotin stabilizer and/or one package stabilizer (QHL-2000).
Preferable, described coupling agent is NDZ-201.
Preferable, described lubricant is calcium stearate, sodium stearate and/or Zinic stearas.
The invention also discloses a kind of preparation ZnSiO
3Method, comprise following concrete steps:
Take by weighing the zinc sulfate dissolved in distilled water, be configured to the solution of 0.2mol/L; Take by weighing water glass and be configured to the solution of 0.2mol/L equally; The zinc sulfate of 0.2mol/L was mixed under the high-speed stirring of electric mixer with the sodium silicate solution of 0.2mol/L in 1: 1 in molar ratio, and reaction 1h is with suction filtration machine suction filtration, vacuum-drying under 70 ℃ of temperature, through fully grinding, cross 80 mesh standard sieves, obtain the zinc silicate sample drying and preserve standby.
Advantage of the present invention is: composite flame-retardant agent is very little to the influence of PVC mechanical property, and low toxicity, meets the trend of current environmental protection, and is simple to operate, cheap, reduced production cost.
Description of drawings
Fig. 1 is the operational flowchart of the specific embodiment of the invention.
Fig. 2 is elongation at break figure.
Fig. 3 is tensile strength figure.
Fig. 4 is the contrast oxygen index.
Fig. 5 is horizontal firing.
Fig. 6 is vertical combustion.
Fig. 7 is that PVC blank sample heat is analyzed.
Fig. 8 is that PVC (composite flame-retardant agent 20g) sample heat is analyzed.
Fig. 9 is that PVC (magnesium hydroxide 20g) sample heat is analyzed.
Figure 10 is that PVC (zinc silicate 20g) sample heat is analyzed.
Figure 11 is the contrast thermogravimetric analysis.
Embodiment
ZnSiO in following examples
3Synthetic method be: take by weighing 28.756g zinc sulfate dissolved in distilled water, change quantitative in the 500ml volumetric flask, be configured to the solution of 0.2mol/L.Take by weighing the 28.422g water glass and be configured to the solution of 0.2mol/L equally.The zinc sulfate of 0.2mol/L was mixed under the high-speed stirring of electric mixer with the sodium silicate solution of 0.2mol/L in 1: 1 in molar ratio, and reaction 1h is with suction filtration machine suction filtration, vacuum-drying under 70 ℃ of temperature, through fully grinding, cross 80 mesh standard sieves, obtain the zinc silicate sample drying and preserve standby.
Needed medicine is listed in shown in the table 1 in following examples.
Table 1 experimental drug
Needed instrument is listed in table 2 in following examples.
Table 2 laboratory apparatus
Experimental procedure in following examples is with shown in Figure 1.
Embodiment 1:
Experiment prepares 5 samples altogether, and the consumption that label is respectively composite flame-retardant agent in 0,1,2,3 and 4,5 sample sees Table 4, and the consumption of all the other compositions sees Table 3.
According to the consumption of each composition in the table 3, after each composition mixed,, extrude at 140 ℃-160 ℃ mixing 15min down with twin screw extruder, namely make the PVC that flame retardant properties is improved.
Table 3 batching consumption situation
Performance test:
1, mechanical property characterizes
Above-mentioned extrudate prepares according to GBT-1039-92 plastics mechanical test method general provisions, use universal testing machine, change the anchor clamps of stretching experiment, at probe temperature (20 scholar 5) ℃, humidity 65%, maximum load 500N is under the draw speed 50mm/min, sample is stretched, broken until sample.
As Fig. 2 and table 4 as can be known, increase fire retardant after, the PVC elongation at break descends again after beginning to raise, and raise to some extent on the whole, but amplitude is little.The PVC sample breakage elongation that does not add fire retardant is 602%, and when the composite flame-retardant agent addition was 20g, elongation at break was 607%, and when the composite flame-retardant agent addition was 25g, elongation at break was 604%, and is very little with PVC sample gap.
Table 4 elongation at break
By Fig. 3 and table 5 as can be known, add composite flame-retardant agent after, the PVC tensile strength descends to some extent, when addition was 20g, tensile strength was 19.14MPa, and when the composite flame-retardant agent addition was 25g, tensile strength but dropped to 18.28MPa, drop is very big.Illustrate that tensile strength declines by a big margin, and begins to influence its mechanical property when composite flame-retardant agent greater than 20g the time.
Table 5 tensile strength
2, combustionproperty characterizes
The horizontal vertical combustion method refers to level or vertical sample one end of clamping, and the sample free end is applied the gas flame of regulation, by measure linear combustionvelocity (horizontal method) and flame is arranged or the flameless combustion time (normal beam technique) is estimated the combustionproperty of sample.This experiment is measured with horizontal vertical combustion instrument according to the GBT-2408-1996 standard.
Oxygen index (OI) refers to that under defined terms material carries out the required minimum oxygen concn of flaming combustion in oxygen-nitrogen mixture stream.Numerical value with the shared percent by volume of oxygen is represented.This experiment uses automatic oxygen index instrument to carry out limiting oxygen index determination according to the GBT-2406.2-2009 standard.
Heat analysis refers under temperature programmed control the physical properties of measurement of species and the analytical technology of temperature relation.This experiment is to make protection gas and sweep gas with nitrogen, and temperature rise rate is 10 ℃/min.
2.1 contrast oxygen index analysis
Table 6 sample oxygen index
By Fig. 4 and table 6 as can be seen, along with the increase of flame retardant agent content, the oxygen index of three kinds of samples all has raising in various degree, especially adds the sample of zinc silicate, illustrates that the zinc silicate flame retardant properties is fine.Answered the sample that closes fire retardant but add, though the inside zinc silicate content is very low, but when the composite flame-proof agent content is 10g, oxygen index just reaches 27.6, when the composite flame-proof agent content is 15g, oxygen index is 30.5, has reached the standard of nonflammable material fully, and exists the cooperative flame retardant effect between explanation zinc silicate and the magnesium hydroxide.
2.2 horizontal firing analysis
Table 7 horizontal firing
By Fig. 5 and table 7 as can be known, increase along with the composite flame-proof agent content, residue length is increasing after the sample combustion, show that horizontal firing speed is more little, when the composite flame-retardant agent addition is 20g, the sample residue length is 89.04mm, has reached the standard of the plastics combustionproperty testing method nonflammable material FH-1 of national regulation.
2.3 vertical combustion analysis
Table 8 vertical combustion
By Fig. 6 and table 8 as can be known, along with the increase of composite flame-proof agent content, the vertical combustion time of sample is more and more littler, and every group combustion time all less than 10s, reached fire retardant material FV-0 and required standard.
2.4 heat is analyzed
Fig. 7-11 provided soft pvc and the PVC sample handled through fire retardant in air from thermogravimetric (TG) curve and the differential scanning calorimetry gained DSC curve of room temperature to 800 ℃.By Fig. 7-11 as can be known, the thermal destruction of PVC is by about room temperature to 350 ℃, and is weightless serious, mainly is because PVC takes off HCl and causes.From Fig. 7-11 as can be seen, behind the adding composite flame-retardant agent, effective starting temperature T of sample
1%Than PVC blank sample and the sample that adds single fire retardant in advance, the adding of composite flame-retardant agent be described, be conducive to PVC more morning deviate from HCl, to fire-retardant favourable.From weight loss, from about room temperature to 350 ℃, add fire retardant after, the weight loss of sample is little compared with the PVC blank sample, but the sample weight loss rate that adds composite flame-retardant agent does not reduce, and maximum weight loss rate is accelerated, and the weightless temperature scope is less, all better than the sample that adds single fire retardant, the adding of composite flame-retardant agent is described, sample is taken off HCl stronger katalysis, is conducive to the slough a large amount of HCls of PVC than morning, promote that getting up early is cross-linked into charcoal, improve surplus charcoal rate and the OI of sample.From the DSC curve, the DSC curve of PVC blank sample and the difference of the DSC curve of composite flame-proof sample are obvious, and the DSC curve of fire-retardant sample is steeper, illustrates that the oxidizing reaction that remains charcoal in certain temperature range is violent and heat release is obvious.The T of fire-retardant sample
mObviously improve than PVC, show to add that the stability of the surplus charcoal of sample obviously improves behind the composite flame-retardant agent, favourable to improving OI.
Claims (8)
1. the composite flame-retardant agent that can improve the PVC flame retardant properties is characterized in that: by ZnSiO
3With Mg (OH)
2Form, and ZnSiO
3: Mg (OH)
2Mass ratio be 1: 9.
2. the application method of the described composite flame-retardant agent of claim 1, concrete operations are as follows:
After polyvinyl chloride resin, softening agent, stablizer, coupling agent, lubricant and described composite flame-retardant agent mixed,, extrude at 140 ℃-160 ℃ mixing 15min down with twin screw extruder.
3. method as claimed in claim 2, wherein, each material consumption is scored by weight and is not: 100 parts of polyvinyl chloride resins, 40 parts in softening agent, 1 part of stablizer, 1 part of coupling agent, 1 part of lubricant and described composite flame-retardant agent 10-25 part.
4. method as claimed in claim 2, wherein, described softening agent is dioctyl phthalate (DOP).
5. method as claimed in claim 2, wherein, described stablizer is organotin stabilizer and/or one package stabilizer QHL-2000.
6. method as claimed in claim 2, wherein, described coupling agent is NDZ-201.
7. method as claimed in claim 2, wherein, described lubricant is calcium stearate, sodium stearate and/or Zinic stearas.
8. composite flame-retardant agent as claimed in claim 1 is characterized in that described ZnSiO
3Prepared by following steps:
Take by weighing the zinc sulfate dissolved in distilled water, be configured to the solution of 0.2mol/L; Take by weighing water glass and be configured to the solution of 0.2mol/L equally; The zinc sulfate of 0.2mol/L was mixed under the high-speed stirring of electric mixer with the sodium silicate solution of 0.2mol/L in 1: 1 in molar ratio, and reaction 1h is with suction filtration machine suction filtration, vacuum-drying under 70 ℃ of temperature, through fully grinding, cross 80 mesh standard sieves, obtain the zinc silicate sample drying and preserve standby.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310183033XA CN103232654A (en) | 2013-05-10 | 2013-05-10 | Composite flame retardant capable of improving flame retardant property of PVC and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310183033XA CN103232654A (en) | 2013-05-10 | 2013-05-10 | Composite flame retardant capable of improving flame retardant property of PVC and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103232654A true CN103232654A (en) | 2013-08-07 |
Family
ID=48880729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310183033XA Pending CN103232654A (en) | 2013-05-10 | 2013-05-10 | Composite flame retardant capable of improving flame retardant property of PVC and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103232654A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524929A (en) * | 2013-09-30 | 2014-01-22 | 芜湖航天特种电缆厂 | Waterproof flame-retardant PVC cable sheath material and preparation method thereof |
| CN105001446A (en) * | 2015-05-11 | 2015-10-28 | 镇江荣诚管业有限公司 | Composite flame retardant for pipe |
| CN105064661A (en) * | 2015-07-20 | 2015-11-18 | 江苏锐升新材料有限公司 | PVC composite floorboard with high-strength wear-resistant layer structure |
| CN105255063A (en) * | 2015-11-17 | 2016-01-20 | 王芳 | Preparing method for flame-retardant PVC power cable |
| CN107298950A (en) * | 2017-07-14 | 2017-10-27 | 国网冀北电力有限公司秦皇岛供电公司 | One kind fire prevention arc resistant adhesive tape and preparation method thereof and construction method |
| CN107739483A (en) * | 2017-11-13 | 2018-02-27 | 苏州亨利通信材料有限公司 | A kind of oxygen index (OI) evaluation method of plasticizer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3816367A (en) * | 1971-06-12 | 1974-06-11 | M & T Chemicals Inc | Flame retardant compositions |
| JPS5659856A (en) * | 1979-10-22 | 1981-05-23 | Dainichi Nippon Cables Ltd | Flame-retardant composition |
| CN1302828A (en) * | 1999-10-28 | 2001-07-11 | 动昉产业株式会社 | Fire retardant polyolefin foamed body composition and its manufacturing method |
-
2013
- 2013-05-10 CN CN201310183033XA patent/CN103232654A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3816367A (en) * | 1971-06-12 | 1974-06-11 | M & T Chemicals Inc | Flame retardant compositions |
| JPS5659856A (en) * | 1979-10-22 | 1981-05-23 | Dainichi Nippon Cables Ltd | Flame-retardant composition |
| CN1302828A (en) * | 1999-10-28 | 2001-07-11 | 动昉产业株式会社 | Fire retardant polyolefin foamed body composition and its manufacturing method |
Non-Patent Citations (3)
| Title |
|---|
| 刘元伟 等: "一种新型复合阻燃剂的制备及性能研究", 《应用化工》, vol. 42, no. 4, 28 April 2013 (2013-04-28), pages 641 - 646 * |
| 屈红强 等: "ZnO与Mg(OH)2在软PVC中的协同阻燃消烟作用", 《塑料科技》, no. 6, 22 December 2005 (2005-12-22), pages 12 * |
| 郭梦金 等: "硅酸盐对软PVC阻燃性和热性能的影响", 《塑料科技》, vol. 35, no. 10, 31 October 2007 (2007-10-31), pages 59 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524929A (en) * | 2013-09-30 | 2014-01-22 | 芜湖航天特种电缆厂 | Waterproof flame-retardant PVC cable sheath material and preparation method thereof |
| CN103524929B (en) * | 2013-09-30 | 2016-05-18 | 芜湖航天特种电缆厂 | A kind of waterproof flame retardant PVC cable jacket material and preparation method thereof |
| CN105001446A (en) * | 2015-05-11 | 2015-10-28 | 镇江荣诚管业有限公司 | Composite flame retardant for pipe |
| CN105064661A (en) * | 2015-07-20 | 2015-11-18 | 江苏锐升新材料有限公司 | PVC composite floorboard with high-strength wear-resistant layer structure |
| CN105255063A (en) * | 2015-11-17 | 2016-01-20 | 王芳 | Preparing method for flame-retardant PVC power cable |
| CN107298950A (en) * | 2017-07-14 | 2017-10-27 | 国网冀北电力有限公司秦皇岛供电公司 | One kind fire prevention arc resistant adhesive tape and preparation method thereof and construction method |
| CN107739483A (en) * | 2017-11-13 | 2018-02-27 | 苏州亨利通信材料有限公司 | A kind of oxygen index (OI) evaluation method of plasticizer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103232654A (en) | Composite flame retardant capable of improving flame retardant property of PVC and application thereof | |
| CN103881229A (en) | High-flame-retardant and halogen-free polyolefin cable material and preparation method thereof | |
| CN104558868A (en) | Preparation method of corrosion-resistant flame-retardant cable rubber material | |
| CN103172938B (en) | Preparation method of non-halogen flame-retardant ethylene propylene diene monomer-polypropylene composite material | |
| CN106380734A (en) | CMR or CMP graded flame retardant cable material | |
| CN111040333B (en) | High-temperature-resistant polyvinyl chloride/nitrile rubber composite cable material | |
| CN104277407A (en) | Anti-yellowing halogen-free flame retardant cable material and preparation method thereof | |
| CN102911470A (en) | High-temperature-resistant fireproof shielded cable material and preparation method thereof | |
| CN102911467A (en) | Tensile, waterproof, double-shielding control cable material and preparation method of tensile, waterproof, double-shielding control cable material | |
| CN108003444B (en) | Low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof | |
| CN107987412B (en) | Low-smoke high-flame-retardant PVC electrical casing | |
| CN101407605A (en) | Expansion flame-retardant material of polyethylene and copolymer thereof | |
| CN103087394A (en) | LSOH (Low Smoke Zero Halogen) flame-retardant cable material | |
| CN103613831A (en) | Nanometer environmental-protection halogen-free fire-retardation insulation material and preparation method thereof | |
| CN103131110A (en) | Inflaming retarding poly carbonate(PC)/poly styrene (PS) mixed alloy materials and manufacture method and purpose thereof | |
| CN104448607B (en) | A kind of high fire prevention PVC-U pipe and preparation method thereof | |
| CN102417653B (en) | Low smoke, zero halogen and flame retardant plastic and production method thereof | |
| CN109206786A (en) | A kind of high-flame-retardant polyvinyl and preparation method thereof | |
| CN104448490A (en) | Halogen-free intumescent flame-retardant polyethylene cable material and preparation method thereof | |
| RU2483377C1 (en) | Electrically insulating composition | |
| CN110760139B (en) | High-resistivity flame-retardant polyvinyl chloride cable material composition | |
| CN103709543A (en) | Low-smoke-and-halogen flame-retardant polyvinyl chloride cable material | |
| CN111138657B (en) | Terpolymer resin | |
| CN105111562A (en) | High-temperature-resistant flame-retardant cable material | |
| CN103333417A (en) | Intumescent halogen-free flame retardant high isotactic polybutene-1 material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130807 |