CN105504597A - Fire retardant for PVC material of cable - Google Patents
Fire retardant for PVC material of cable Download PDFInfo
- Publication number
- CN105504597A CN105504597A CN201610061380.9A CN201610061380A CN105504597A CN 105504597 A CN105504597 A CN 105504597A CN 201610061380 A CN201610061380 A CN 201610061380A CN 105504597 A CN105504597 A CN 105504597A
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- Prior art keywords
- fire
- aluminium titanates
- colloidal sol
- retardant
- cerium oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
Abstract
The invention discloses a novel fire retardant for a PVC material of a cable. The fire retardant comprises aluminium titanate-cerium oxide and the consumption of the fire retardant is 1-10 wt% of the total weight of the PVC material, wherein aluminium titanate-cerium oxide can be used together with other conventional PVC material fire retardants and has relatively high flame retardancy, and the oxygen index can be above 35. The novel fire retardant has the characteristics of being low in addition and environmentally friendly.
Description
Technical field
The invention belongs to cable special PVC additive, particularly relate to a kind of fire retardant of cable PVC material.
Background technology
Polyvinyl chloride (PVC) resin, as the time-honored thermoplastics of one, has a wide range of applications at wires and cables industry.The electric wire of the 450V/750V such as lived now and following insulation and flexible cord all much use PVC as matrix resin.Along with flame retarding PVC composition for cable is in the widespread use in the fields such as electronic apparatus, computer, automobile and space flight, also there is more and more higher requirement to the flame retardant resistance of cable.
PVC cable is owing to being wherein mixed with a large amount of softening agent and other auxiliary agents, and its flame resistivity is not enough, and can produce harmful HCl gas when burning, HCl also can have very strong corrosive nature to metal.Except producing toxic gas, also not exclusively can produce a large amount of smog because of some gaseous combustions, drastically influence the safety of life and property of the people.Therefore, research and develop low cigarette, the PVC cable of low toxicity becomes the urgent demand of cable-flame retardant industry, there is important social value.
In PVC cable, we adopt the method adding fire retardant and flame-retardant plasticizer to realize its fire-retardant and but effect of cigarette usually.The method of concrete use has following several: (1) substitutes conventional softening agent with fire-retardant softening agent.Such as often use triaryl phosphate and alkyl diaryl phosphate as softening agent, their thermolysiss when burning generate not volatile Tripyrophosphoric acid, can form layer protecting film at solid surface, cut off the contact with oxygen.(2) inorganic combustion inhibitor such as antimony compounds, metal hydroxides is added.Usually but the aluminium hydroxide added also has significantly cigarette effect.(3) method simultaneously adding flame-retardant plasticizer, inorganic combustion inhibitor and fire-retardant filler is adopted when plasticizer loading is higher.(4) usually also smoke suppressant is added.Be mainly used in PVC cable material press down cigarette have molybdic oxide and ammonium octamolybdate etc.In the formula of PVC cable material, we often need to select suitable flame-retardant plasticizer and the proportioning of Conventional plasticizers according to the different purposes of CABLE MATERIALS and fire-retardant demand, can reach high cost performance like this.
The flame retardant properties of PVC cable material is normally weighed with oxygen index, oxygen index refer to allow sample burn required for minimum oxygen concn.When oxygen index is larger, flame retardant resistance is higher.The material of usual oxygen index more than 30 just has certain flame retardant resistance.
Al (OH) is added in PVC cable material
3, Sb
2o
3, the inorganic combustion inhibitors such as zinc borate (ZB), their the flame retardant properties impact of consumption on PVC is very large.Along with Sb
2o
3increase, the limiting oxygen index(LOI) linearly ascendant trend of PVC cable material, at nanometer Sb
2o
3addition when being greater than 1.5 parts, nanometer Sb
2o
3micron order Sb is greater than to the oxygen index contribution of PVC
2o
3.But due to Sb
2o
3price comparison is expensive, so generally add Sb
2o
3amount be not very high, as long as can certain flame retardant resistance be ensured.And the ZB added can be used as smoke suppressor, by ZB and Sb
2o
3compound use also has low raw smoke which by making PVC cable material while having suitable oxygen index.
Summary of the invention
The present inventor proposes using aluminium titanates-cerium oxide as superpolymer especially PVC material fire retardant first, described aluminium titanates-cerium oxide can with other conventional PVC material fire retardant with the use of, there is higher fire retardancy, oxygen index can reach more than 35, there is addition little, environment amenable feature.
Technical scheme of the present invention is achieved in the following ways:
The invention discloses a kind of novel cable PVC material fire retardant, this fire retardant comprises aluminium titanates-cerium oxide, and its consumption is the 1-10wt% of PVC material gross weight, is more preferably 3-5wt%.
The particle diameter of described aluminium titanates-cerium oxide fire-retardant particles is the fire-retardant particles of 10-100 micron.
The preparation method of described aluminium titanates-cerium oxide fire-retardant particles, comprises the steps: aluminum nitrate to be dissolved in ethanol to form aluminum nitrate ethanolic soln; Tetrabutyl titanate is dissolved in ethanol and forms tetrabutyl titanate ethanolic soln, and in described tetrabutyl titanate ethanolic soln, adds the methyl ethyl diketone of tetrabutyl titanate quality 20-80%, vigorous stirring 10-30min; By aluminium, titanium mol ratio 2:1, the aluminum nitrate ethanolic soln prepared slowly is joined in tetrabutyl titanate ethanolic soln; Adding nitric acid regulates mixed solution pH value to 5-7, and finally add polyoxyethylene glycol and make dispersion pore-forming material, consumption is the 0.5-5% of solvent volume, and vigorous stirring obtains aluminium titanates colloidal sol; Soluble in water with cerous nitrate, forming the cerous nitrate aqueous solution, is that precipitation agent is according to Ce and CO with ammonium bicarbonate aqueous solution
3 2-mol ratio 1:2-3 mixes, and adds the polyoxyethylene glycol of mixing solutions quality 1-2% as dispersion agent, vigorous stirring 10-30min simultaneously, obtains cerous carbonate colloidal sol; Aluminium titanates colloidal sol and cerous carbonate colloidal sol are mixed according to the ratio that Ce and Al mol ratio is 0.1-10, and after vigorous stirring 10-30min, suction filtration is dry, dry 1-5h at 500-700 DEG C, pulverizes in ball mill and obtain described aluminium titanates-cerium oxide fire-retardant particles.
The molecular weight of described polyoxyethylene glycol is 200-4000.
Preferred described aluminium titanates colloidal sol and cerous carbonate colloidal sol are the ratio mixing of 0.5-2 according to Ce and Al mol ratio.
Described methyl ethyl diketone is titanium hydrolysis inhibitor, and methyl ethyl diketone can form stable Ti chelator structure with titanium chelating, effectively suppresses the hydrolysis of titanium, ensures that the aluminium titanates colloidal sol generated is even, has good adsorptive power.
The present invention is as follows relative to the beneficial effect of prior art:
The beneficial effect adopting technique scheme to produce is: develop the purposes of aluminium titanates-cerium oxide as superpolymer especially PVC material fire retardant, have developed new superpolymer inorganic combustion inhibitor; (2) aluminium titanates-cerium oxide that the present invention adds small amount (1-10wt.%) can reach flame retardant effect (oxygen index LOI >=40), compared with prior art, there is addition few, low to the mechanical property deterioration degree of material, even can also improve the elongation at break of material;
Embodiment
Be described in detail below in conjunction with the technical scheme of specific embodiment to invention.
The preparation of aluminium titanates-cerium oxide fire-retardant particles: aluminum nitrate is dissolved in ethanol and forms aluminum nitrate ethanolic soln; Tetrabutyl titanate is dissolved in ethanol and forms tetrabutyl titanate ethanolic soln, and in described tetrabutyl titanate ethanolic soln, adds the methyl ethyl diketone of tetrabutyl titanate quality 20%, vigorous stirring 10-30min; By aluminium, titanium mol ratio 2:1, the aluminum nitrate ethanolic soln prepared slowly is joined in tetrabutyl titanate ethanolic soln; Add nitric acid and regulate mixed solution pH value to 7, finally add polyoxyethylene glycol and make dispersion pore-forming material, consumption is 1% of solvent volume, and vigorous stirring obtains aluminium titanates colloidal sol; Soluble in water with cerous nitrate, forming the cerous nitrate aqueous solution, is that precipitation agent is according to Ce and CO with ammonium bicarbonate aqueous solution
3 2-mol ratio 1:2 mixes, and adds the polyoxyethylene glycol of mixing solutions quality 1% as dispersion agent, vigorous stirring 30min simultaneously, obtains cerous carbonate colloidal sol; Aluminium titanates colloidal sol and cerous carbonate colloidal sol are mixed according to the ratio that Ce and Al mol ratio is 1, and after vigorous stirring 10min, suction filtration is dry, dry 5h at 550 DEG C, pulverizes in ball mill and obtain described aluminium titanates-cerium oxide fire-retardant particles.
Embodiment 1
Add described aluminium titanates-cerium oxide fire retardant at PVC superpolymer, consumption is 5wt%.
Embodiment 2
Add described aluminium titanates-cerium oxide fire retardant at PVC superpolymer, consumption is 2wt%.
Comparative example 1
Do not add aluminium titanates-cerium oxide fire retardant, other component is identical with embodiment 1
Performance test:
By the basic recipe corresponding to each embodiment, conveniently consumption and formula add other additive, as softening agent (DOP), organotin stabilizer, coupling agent, calcium stearate, stearic acid, then by even for said components mechanical stirring in high-speed mixer, mixing and be pressed into standard-sized sample on double track mixing roll.And according to ASTMD2863-2000, oxygen index test is carried out to sample.
| Oxygen index | Flame retarding efficiency | |
| Embodiment 1 | 36 | 1.5 |
| Embodiment 2 | 38 | 1.6 |
| Comparative example 1 | 21 | 0.1 |
As can be seen from Table 1, compare with blank PVC material, the sample oxygen index that with the addition of aluminium titanates-cerium oxide fire retardant significantly improves, and along with the increase of consumption, oxygen index also increases.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.All embodiments of the present invention all can only be thought explanation of the present invention instead of restriction, every any trickle amendment done by technology contents of the present invention or equivalently to replace, and all belong within technical scheme of the present invention.
Claims (5)
1. a novel cable PVC material fire retardant, this fire retardant comprises aluminium titanates-cerium oxide, and its consumption is the 1-10wt% of PVC material gross weight, is more preferably 3-5wt%.
2. fire retardant according to claim 1, is characterized in that the particle diameter of described aluminium titanates-cerium oxide fire-retardant particles is the fire-retardant particles of 10-100 micron.
3. prepare a method for aluminium titanates-cerium oxide fire-retardant particles as claimed in claim 1 or 2, comprise the steps: aluminum nitrate to be dissolved in ethanol to form aluminum nitrate ethanolic soln; Tetrabutyl titanate is dissolved in ethanol and forms tetrabutyl titanate ethanolic soln, and in described tetrabutyl titanate ethanolic soln, adds the methyl ethyl diketone of tetrabutyl titanate quality 20-80%, vigorous stirring 10-30min; By aluminium, titanium mol ratio 2:1, the aluminum nitrate ethanolic soln prepared slowly is joined in tetrabutyl titanate ethanolic soln; Adding nitric acid regulates mixed solution pH value to 5-7, and finally add polyoxyethylene glycol and make dispersion pore-forming material, consumption is the 0.5-5% of solvent volume, and vigorous stirring obtains aluminium titanates colloidal sol; Soluble in water with cerous nitrate, forming the cerous nitrate aqueous solution, is that precipitation agent is according to Ce and CO with ammonium bicarbonate aqueous solution
3 2-mol ratio 1:2-3 mixes, and adds the polyoxyethylene glycol of mixing solutions quality 1-2% as dispersion agent, vigorous stirring 10-30min simultaneously, obtains cerous carbonate colloidal sol; Aluminium titanates colloidal sol and cerous carbonate colloidal sol are mixed according to the ratio that Ce and Al mol ratio is 0.1-10, and after vigorous stirring 10-30min, suction filtration is dry, dry 1-5h at 500-700 DEG C, pulverizes in ball mill and obtain described aluminium titanates-cerium oxide fire-retardant particles.
4. method as claimed in claim 3, is characterized in that the molecular weight of described polyoxyethylene glycol is 200-4000.
5. method as claimed in claim 3, is characterized in that described aluminium titanates colloidal sol and cerous carbonate colloidal sol are preferably the ratio mixing of 0.5-2 according to Ce and Al mol ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610061380.9A CN105504597B (en) | 2016-01-29 | 2016-01-29 | A kind of cable PVC material fire retardant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610061380.9A CN105504597B (en) | 2016-01-29 | 2016-01-29 | A kind of cable PVC material fire retardant |
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|---|---|
| CN105504597A true CN105504597A (en) | 2016-04-20 |
| CN105504597B CN105504597B (en) | 2017-12-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610061380.9A Active CN105504597B (en) | 2016-01-29 | 2016-01-29 | A kind of cable PVC material fire retardant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885465A (en) * | 2016-05-18 | 2016-08-24 | 无为县金华电缆材料有限公司 | Formula of ultraviolet-resistant waterproof cable armored layer |
| CN115287005A (en) * | 2022-09-01 | 2022-11-04 | 柳州市来柳金属钢结构有限公司 | Flame-retardant PVC adhesive tape |
Citations (4)
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| CN103113649A (en) * | 2013-02-02 | 2013-05-22 | 金发科技股份有限公司 | Flame retardant polyolefin and preparation method and product thereof |
| CN103897215A (en) * | 2012-12-26 | 2014-07-02 | 金发科技股份有限公司 | Composite fire retardant and use thereof |
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| CN105131579A (en) * | 2015-09-21 | 2015-12-09 | 安徽徽宁电器仪表集团有限公司 | Oil-proof fireproof soft cable material for oil-immersed pump and preparation method of oil-proof fireproof soft cable material |
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2016
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Patent Citations (4)
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| CN104487501A (en) * | 2012-03-20 | 2015-04-01 | 罗地亚经营管理公司 | Flame retardant polymer compositions |
| CN103897215A (en) * | 2012-12-26 | 2014-07-02 | 金发科技股份有限公司 | Composite fire retardant and use thereof |
| CN103113649A (en) * | 2013-02-02 | 2013-05-22 | 金发科技股份有限公司 | Flame retardant polyolefin and preparation method and product thereof |
| CN105131579A (en) * | 2015-09-21 | 2015-12-09 | 安徽徽宁电器仪表集团有限公司 | Oil-proof fireproof soft cable material for oil-immersed pump and preparation method of oil-proof fireproof soft cable material |
Non-Patent Citations (2)
| Title |
|---|
| F 维拉尼等: "《稀土技术及应用》", 31 July 1986, 烃加工出版社，1986年7月北京第1版 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885465A (en) * | 2016-05-18 | 2016-08-24 | 无为县金华电缆材料有限公司 | Formula of ultraviolet-resistant waterproof cable armored layer |
| CN115287005A (en) * | 2022-09-01 | 2022-11-04 | 柳州市来柳金属钢结构有限公司 | Flame-retardant PVC adhesive tape |
| CN115287005B (en) * | 2022-09-01 | 2024-05-03 | 东莞市恒创胶粘制品有限公司 | Flame-retardant PVC adhesive tape |
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| Publication number | Publication date |
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| CN105504597B (en) | 2017-12-26 |
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| CB03 | Change of inventor or designer information |
Inventor after: Lin Guangyao Inventor before: Hao Fu |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171114 Address after: 315600, Zhejiang province Ningbo city Ninghai County Qiaotou Hu Street Wen Xi Zhou Industrial Zone Applicant after: Ningbo times billion electric technology Limited by Share Ltd Address before: 266000 Shandong province Qingdao City, Inner Mongolia Road No. 30 Building No. 5 Applicant before: Hao Fu |
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