Electrically insulating composition

FIELD: electricity.

SUBSTANCE: electrically insulating composition consisting of suspension polyvinylchloride, ester and, when required, phosphate plasticiser, lead or calcium-zinc stabiliser, antioxidant, antimony oxide, zinc oxide, zinc borate, epoxidated vegetable oil comprises additionally sized aluminium hydrate or magnesium hydrate or their mixture, sized calcium carbonate, sized calcium-magnesium hydroxycarbonate and calcium-aluminium hydroxycarbonate at certain ratio of component.

EFFECT: reduced toxicity, corrosion activity and fume emission.

2 cl, 1 tbl, 1 ex

 

The invention relates to a cable technique, namely to polymeric compositions based on plasticized PVC, and can be used in the manufacture of wires and cables, operating in conditions of high fire risk in buildings, transport and communications, etc.

The compositions for wire and cable shall ensure properties such as low Flammability, smoke generation, toxicity and corrosiveness.

To ensure lower Flammability and smoke emission in the composition is injected flame retardants and damodarastaka, which usually use an oxide of antimony (Sb2O3), hydroxides of aluminum and magnesium (Al(OH)3and Mg(OH)2), various derivatives of zinc oxide, borate, stannate and so on).

The toxicity and corrosiveness of the PVC compositions depend on the selection in the event of fire carbon monoxide (CO) and hydrogen chloride (HCl), to inhibit this process, enter carbonate fillers and carbonitride agents (e.g., phosphorus - and boron-derivative).

The prior art insulating composition intended for insulation of cables and wires, including

suspension PVC 100,

ester plasticizer 40-80,

lead stabilizer 3-7,

calcium carbonate 30-500,

aluminum hydroxide 10-100,

XID antimony 4-7,5,

zinc oxide 0,7-1,9,

boric acid of 0.4-0.6,

BHT 0.1 to 0.6,

the diphenylolpropane 0,1-0,6

(EN 2195729 C1, CL NW 3/44, H01B 7/295, C08L 27/06, publ. 27.12.2002).

This solution has sufficient resistance to combustion - values KI level 33-34%.

The disadvantage of the considered electrical insulating composition is the level of smoke (maximum optical density of smoke - Dmax - 170-215) and allocation of HCl (8.0 to 10.6 percent), which does not correspond to modern requirements of low fireproof materials.

The prior art insulating composition intended for insulation of cables and wires, including

suspension PVC 100,

ester plasticizer 30-70,

lead stabilizer (trehosnovnoy sulfate lead) 3-7,

calcium carbonate 20-300,

aluminum hydroxide 20-70,

the oxide of antimony 3-8,

zinc oxide is 0.5-10,

the zinc borate of 0.5-8,

the zinc stearate 0.25 to 4

(EN 2256968 C1, CL H01B 3/44, publ. 20.07.2005).

The disadvantage of the considered electrical insulating composition is the level of smoke (maximum optical density of smoke - Dmax - 170-185) and allocation model HC1 (6.5 to 9.8 per cent), which does not correspond to modern requirements of low fireproof materials.

The above insulating composition p is establet a composition based on suspension PVC, ester plasticizers and lead stabilizers. This combination products such as antimony oxide, zinc oxide (ZnO), boric acid or zinc borate, aluminum hydroxide and calcium carbonate can reduce the fire risk.

The closest analogue to the claimed insulating composition is a polymer composition for a cable flexible PVC, which includes

suspension PVC 100,

ester plasticizer 15-80,

the phosphate plasticizer 5-40,

lead stabilizer 2-7 in combination with 0.3-5 calcium stearate or lead stearate, or a complex of calcium-zinc stabilizer 3-10,

calcium carbonate 20-150,

magnesium carbonate is 0-100,

zinc oxide is 0.3-10,

the aluminum hydroxide or magnesium hydroxide or a mixture in the ratio 1:1 15-90,

the oxide of antimony 0-5,

the zinc borate 0.5 to 15,

boric acid is 0.1-2,

the diphenylolpropane 0,1-1,

chlorinated polyethylene 0-20,

calcium oxide or hydroxide of 0.5-10,

bromide organic compound 0-15,

epoxy resin or epoxydecane vegetable oil 0-5,

dipentaerythritol or pentaerythritol 0-2

(EN 2488608 C1, CL C08L 27/06, publ. 27.07.2013).

In this polymer composition reached lower, compared with the previous songs, smoke (Dmax 95-129 combustion and 115-148 when corruption) and increased thermostability. Not what the rest of it is high secretion of HCl and CO (75-93 mg/g and 52-56 mg/g), which does not comply with stricter modern requirements to reduce the toxicity and corrosiveness of polymeric materials.

To reduce the smoke emission in this polymer composition were introduced (phosphate plasticizers) or used in larger quantities (boric acid) components that cause dehydrochlorination of PVC, and to resolve this effect and improve thermal stability of the used additional stabilizers (oxide or calcium hydroxide, pentaerythritol or dipentaerythritol, epoxy resin or epoxydecane vegetable oil). This circumstance gave unwanted side effects.

Due to the fact that some of these components are hydrophilic (boric acid, oxide or hydroxide of calcium, pentaerythritol or dipentaerythritol), the composition has a high moisture absorption, which leads to deterioration of mechanical strength and dielectric properties of insulation and sheath of the cables during operation and even storage.

This contributes to the use of non-finished fillers and flame retardants.

Moreover, even this enhanced stabilization does not provide long-term resistance to thermal aging.

There is a need for technical solutions that would allow along with the reduction of smoke emission decrease of power is pogloshenie and increase resistance to termostatu.

The technical result of the claimed invention is to reduce the toxicity and corrosiveness, reduction of smoke emission and decrease moisture absorption and increase resistance to termostatu.

The technical result is achieved due to the replacement of the insulating composition of hydrophilic and corrosion-active components with new components, namely, hydroxycarbonate calcium-magnesium, hydroxycarbonate calcium-aluminum and antioxidants.

Objective of the claimed invention to provide an insulating composition composition with improved performance characteristics.

The problem is solved by performing electrical insulating composition comprising a suspension polyvinyl chloride, ester and, optionally, a phosphate plasticizer, lead or calcium-zinc stabilizer, if necessary, an antioxidant, optionally, antimony oxide, zinc oxide, optionally, zinc borate, if necessary, epoxydecane vegetable oil.

The composition additionally contains a brushed aluminum hydroxide or magnesium or their mixture, brushed calcium carbonate, finished hydroxycarbonate calcium-magnesium, hydroxycarbonate magnesium-calcium and, if necessary, hydroxycarbonate calcium-aluminum with trail the next ratio of the components, M. including:

- suspension PVC (Kf70-74) 100,

- ester plasticizer - C8-10-alkylphenyl plasticizer 30-70,

phosphate plasticizer - C8-10-alkyl(aryl)phosphate plasticizer 0-20,

- lead or CaZn stabilizer to the desired operating temperature of the cable 5-9,

- antioxidant, phenolic antioxidant, 0-0,5,

- epoxydecane vegetable oil 0-10,

oxide of antimony 0-5,

- zinc oxide 2-10,

- borate zinc 0-10,

- brushed aluminum hydroxide or magnesium or a mixture of 50-200,

- brushed calcium carbonate 50-300,

- if necessary, finished hydroxycarbonate calcium-magnesium 0-100,

- hydroxycarbonate calcium-aluminum 0-10.

As the sizing of the above components of the composition used stearic acid or its substitutes (C15-C18-fatty acids).

Dressing reduces the diffusion rate in the liquid fillers components PVC-compositions (plasticizers, stabilizers).

Fatty acid sizing, in addition to its primary purpose (to improve the distribution of fillers in a polymer matrix), is also a wetting agent that reduces the water absorption of fillers and, due to this, and the whole composition.

The proposed composition contains known and available components:

In ka is este suspension of polyvinyl chloride can be used brand S, Vinnolit S4170, Georgia Gulf GG2110 etc.;

as With8-10-alkylphthalimide plasticizer - Palatinol N, Palatmol Z (BASF), DIDP (Exxon), Witamol 118 (Evonik), etc.;

as With8-10-alkyl-arylphosphate plasticizer - Santicizer 148, Reofos 362, etc.;

as an integrated lead or Ca-Zn stabilizer cable type at the desired operating temperature (70-90°C) - Baeropan TX 296 AC, Baeropan 86 56, Mon. KA-ST, Eurostab CW 0370/ R-4, Stabiol CZ 3046/5, Akropan 2530, etc.;

as the phenolic antioxidant Irganox 1010, Irganox 1076, etc.;

as brushed aluminum hydroxide or magnesium or mixtures thereof - Martinal OL-104/C, Apymag 60S, Empirin With a 3.5, etc.;

as finished of calcium carbonate Omyacarb TKA, Zetafil CSTHT.n.;

as finished hydroxycarbonate calcium-magnesium UltraCarb 1291, etc.;

as hydroxycarbonate calcium-aluminum - Actilox CAHC.

In addition to the above components, the composition may contain additives target for PVC-compositions (pigments, biocides, light stabilizers, lubricants, processing additives, etc.,) in an amount not exceeding 5 m H. (avoid modifying the claimed properties).

Example

Compositions for testing are prepared by mixing the above components in high-speed turbomachine, homogenization and granulating the obtained mixtures in Ko Cneter subsequent processing of the granulate by rolling or EC is tretirovanie.

In the mixer load PVC, stabilizer, antioxidant, stirred for 3-5 minutes, then add plasticizers and epoxydecane vegetable oil and mix until complete absorption of the plasticizer. Then in the mixer sequentially, 2-3 reception, DeGroat flame retardants and fillers (oxide, antimony oxide and zinc borate, hydroxycarbonate calcium-aluminium-calcium-magnesium, aluminium hydroxide or magnesium or their mixture and calcium carbonate) with stirring for 3-5 minutes after each reload.

The resulting mixture was processed in Ko Cneter at a temperature of 160-190°C., the granules plasticity on a laboratory roll mill or a single screw extruder with a flat-Villeroy at a temperature of 2-5°C higher than the temperature of the processing in Ko Cneter.

From the obtained sheet of plastic is made of standard samples for testing.

The compositions were tested in terms of fire: resistance to combustion method CI according to GOST 12.1.044 (sample thickness of 4 mm), maximum optical smoke density (Dmax) allocated to combustion regimes and corruption, according to GOST 24632-81 (sample thickness 1 mm), the amount of emitted during combustion halogenation acid (HCl) according to GOST R IEC 60754-1 and carbon monoxide according to GOST 12.1.044, the toxicity index of the products of combustion (CL50) according to GOST 12.1.044. In addition, predelli water absorption according to GOST R IEC 60811-1-3 and resistance to termostatu.

The compositions and properties of the compositions are given in the table.

The test results indicate the superiority of the proposed composition relative to the prototype: preserved when the level KEY and optical smoke density (Dmax) release of HCl and WITH reduced almost by half, which reduced and the rate of emission during combustion. This allowed to translate it from the category of moderately hazardous materials as low-risk and to use in the manufacture of cables with reduced toxicity. In addition, the proposed composition has a lower water absorption and greater resistance to termostatu, which increases the reliability and durability of cable products in the operation.

NameThe proposed compositionthe composition of the prototype
12345678
Components, m H.:
PVC suspension (KF 70-74)100100100100100100100100
C8-10-alkylphenyl plasticizer50403050457015-80 ester plasticizer15-80 ester plasticizer
C8-10-alkylaromatic plasticizer10205155-40 phosphate plasticizer5-40 phosphate plasticizer
integrated stabilizer67968 52-7 RV stabilizer3-10 Ca-Zn stabilizer
antioxidant0,50,3-0,30,2-0.1-1 diphenylolpropane-
epoxydecane vegetable oil-253-50-50-5
the oxide of antimony32-4150-50-5
zinc oxide6427310the 0.3-10the 0.3-10
the zinc borate5 10-5--0.5 to 150.5 to 15
aluminum hydroxide2050--5010015-90-
magnesium hydroxide30--100-100-15-90
hydroxycarbonate calcium-magnesium-50100-75---
calcium carbonate5070505012520020-15020-150
hydroxycarbonate calcium-aluminum10--55-
magnesium carbonate------0-1000-100
boric acid------0.1 to 20.1 to 2
calcium stearate or lead------0,3-5-
chlorinated polyethylene---- --0-200-20
calcium oxide or hydroxide------0,5-100,5-10
bromide organic fire retardant------0-150-15
dipentaerythritol or pentaerythritol0-20-2
Properties:
KI %35 373436353834-3835-37
Dmax-burning119117125921266295-129100-130
Dmax-corruption12111411310310998108-150115-148
Qty HCl, mg/g49503745302175-9183-93
gCO, mg/g38292635241852*256 *2
N CL50, g/m3*112713513112913816971 *279*2
water absorption (10 days at 70°C)2,04,23,5the 3.8a 4.96,010 *216 *2
the duration of thermostate at 100°C to reduce the relative elongation at break 2 times day80766478716060*230*2
* level selection for high-risk materials - 120-360 mg/g, moderately hazardous - 40-120 mg/d, low risk up to 40 mg/g
*1- norm category of toxicity according to GOST 12.1.044 - moderately hazardous materials 40-120 g/m3, low hazard - more than 120 g/m3
*2- because in the prototype there are no data on toxicity tests, termostate to achieve the maximum operational status insulating material (reduction in relative elongation at break in half), were manufactured and tested examples 3 and 13 of the prototype

1. Insulating composition comprising a suspension polyvinyl chloride, ester and, optionally, a phosphate plasticizer, lead or calcium-zinc stabilizer, if necessary, an antioxidant, optionally, antimony oxide, zinc oxide, optionally, zinc borate, if necessary, epoxydecane vegetable oil, characterized in that it additionally contains a brushed aluminum hydroxide or magnesium or their mixture, brushed calcium carbonate, finished hydroxycarbonate calcium-magnesium and, if necessary, hydroxycarbonate calcium-aluminum in the following ratio of components, m H.:
- suspension PVC (Kf70-74)100,
- ester plasticizer - C8-10-alkylphenyl plasticizer 30-70,
phosphate plasticizer - C8-10-alkyl(aryl)phosphate plasticizer 0-20,
- lead or CaZn stabilizer to the desired operating temperature of the cable 5-9,
- antioxidant, phenolic antioxidant, 0-0,5,
- epoxydecane Rast is positive oil 0-10,
oxide of antimony 0-5,
- zinc oxide 2-10,
- borate zinc 0-10,
- brushed aluminum hydroxide or magnesium or a mixture of 50-200,
- brushed calcium carbonate 50-300,
- finished hydroxycarbonate calcium-magnesium 0-100,
- hydroxycarbonate calcium-aluminum 0-10.

2. Insulating composition under item 1, characterized in that as the sizing of the above components of the composition used stearic acid or its substitutes (C15-C18-fatty acids).



 

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20 cl, 2 tbl, 1 dwg

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11 cl, 7 dwg, 1 ex

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3 cl, 1 tbl, 2 ex

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20 cl, 3 dwg, 2 tbl, 22 ex

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EFFECT: wood-polymer materials based on the obtained highly filled PVC composition have an improved melt flow index, high tensile strength and thermal stability.

1 tbl

FIELD: chemistry.

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EFFECT: improved colour fastness of the composition.

2 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: polymer composition for cable plastic includes polyvinyl chloride, dioctyl phthalate, diphenylol propane, aerosil, tribasic lead sulphate and a stabiliser. The composition is characterised by use of a complex stabiliser - plasticiser, which is a product containing calcium stearate, magnesium stearate and zinc stearate in molar ratio 2:2:1, with acid number of not greater than 5 mg KOH/g in a medium of chlorinated paraffin wax KHP-30 in weight ratio of 1:6, respectively, and additionally agidol and chalk, with the following ratio of components, pts.wt: polyvinyl chloride 100; dioctyl phthalate 37-47; diphenylol propane 0.1; tribasic lead sulphate 3-5.7; agidol 0.08; chlorinated paraffin wax KHP-30 2-14; chalk 11; aerosil 0.7; said stabiliser-plasticiser 0.33-2.33.

EFFECT: obtaining a more processable polymer composition for cable plastic with improved physical and mechanical properties, high thermal stability, wider range of polymer composition stabilisers.

2 tbl, 5 ex

FIELD: composite materials.

SUBSTANCE: invention discloses a method for manufacturing composite material for shielding-mediated protection against electromagnetic emission and can be used in electronics, in radio engineering, and also in a series of special-destination articles. In addition, material may be used for anechoic boxes and in various assemblies of technical devices and radio apparatuses. Method comprises mixing modified graphite-containing conducting filler and polymeric binder at weight ratio (50-80):(20-50). Once ingredients combined, mixture is additionally subjected to thermal expansion in thermal shock mode at 250-310оС and then molded. Polymeric binder is selected from polyolefins, polystyrene, fluoroplastic, polyvinylchloride paste and modified graphite is product obtained by modifying graphite with concentrated sulfuric and nitric acids. Material is characterized by that, in wavelength band from 2 to 5 cm at thickness of material up to 0.1 mm, transmission coefficient is decreased from -40 to -85 dB.

EFFECT: improved performance characteristics.

6 cl, 1 tbl, 2 ex

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