CN101445634A - Polyvinyl chloride cross linking through sulfhydryl compound - Google Patents
Polyvinyl chloride cross linking through sulfhydryl compound Download PDFInfo
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- CN101445634A CN101445634A CNA200810242855XA CN200810242855A CN101445634A CN 101445634 A CN101445634 A CN 101445634A CN A200810242855X A CNA200810242855X A CN A200810242855XA CN 200810242855 A CN200810242855 A CN 200810242855A CN 101445634 A CN101445634 A CN 101445634A
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Abstract
The polyvinyl chloride cross linking method through sulfhydryl compound is an improved polyvinyl chloride cross linking method through sulfhydryl compound. The polyvinyl chloride cross linking method is characterized in that the sulfhydryl compound cross linked polyvinyl chloride comprises 100 parts of PVC resin, 40 to 90 parts of plasticizer, 2 to 6 parts of acid absorbent, 3 to 7 parts of dimercapto-triazine compound cross linking agents, 0.2 to 2 parts of composite catalyst, and the components are blended and vulcanized; the PVC resin comprises the following components: 60 wt% to 80wt% of PVC resin with polymerization degree of 950 to 1,050 and 20wt% to 40wt% of PVC resin with polymerization degree of 2,450 to 2,550; the composite catalyst is formed by blending 60wt% to 80wt% of octadecyl alcohol and 20wt% to 40wt% of thiazolium compound. Compared with the prior art, the polyvinyl chloride cross linking method has the advantages that the vulcanization rate is high, the vulcanization time is reduced to 8 minutes from 15 minutes originally, the cross linking degree is high and improved to 85% from 65% originally, the physical and mechanical performances are good, the tensile strength is improved to 20 MPa from 16 MPa originally, and the rebound elasticity and the low temperature flexibility are also improved.
Description
Technical field
The present invention relates to a kind of crosslinked PVC insulated cable material, especially to the improvement of polyvinyl chloride cross linking through sulfhydryl compound.
Background technology
Polyvinyl chloride (PVC) plastics, have good comprehensive mechanical performance, flame retardant resistance, and cheap, recyclable utilization, thereby be widely used in wire cable insulating or sheath, for example the electric wire polymerization degree commonly used is 950～1050 insulation of PVC do or sheath.But igelite is under higher use temperature (for example 〉=90 ℃) condition, and its performance has very big decline, and for example tensile strength descends, and distortion increases, heat-drawn wire, high temperature dimensional stability variation, and these have all had a strong impact on use range expansion.
Crosslinking reaction can make the new key of formation between the macromolecular chain, make it to become reticulated structure, therefore plastics are carried out crosslinkedization modification, can improve its some performance greatly, for example to the polyethylene crosslinking modification, tensile strength, heat-drawn wire be can improve, dimensional stability, rebound resilience, wear resistance, oil-proofness etc. increased.Obviously the PVC plastics being carried out crosslinkedly, also is to improve tensile strength of material, heat-drawn wire, increase dimensional stability, rebound resilience, wear resistance, oil-proofness.At present the plastics cross-linking method is had: chemically crosslinked, cross-linking radiation, sulfide is crosslinked, and dimercapto-triaizine compounds is crosslinked, crosslinked with silicane.
Pvc material is being subjected to high-energy radiation, and free radical causes and can cause the macromolecular chain rupture of PVC, degraded when crosslinked, and to the material production detrimentally affect, so cross-linking radiation, chemically crosslinked influence the final performance of material because of meeting, and less being employed.The crosslinked rate of crosslinking that exists again of sulfide is slow, and the finished product have the bad smell phenomenon, the also less employing of reality.Crosslinked with silicane needs crosslinkedly in steam or water-soluble environment, and polyvinyl chloride is a polar macromolecule material, and immersion back electrical property can sharply descend, thereby causes the decline of electrical property, and this also is disadvantageous to electric wire.Therefore above-mentioned these cross-linking methods are all less is used.Particularly, above-mentioned cross-linking method, the gained degree of crosslinking is the highest also has only 70%, and degree of crosslinking is low, and the above-mentioned modification of material improves also limited.
Polyvinyl chloride dimercapto-triaizine compounds is crosslinked, be to be undertaken by ionic reaction mechanism, degraded, the serious phenomenon of variable color when not having irradiation and peroxide crosslinking, crosslinking temperature wide ranges, easy to control, rate of crosslinking is controlled, and is therefore crosslinked in polyvinyl chloride by more application.But the crosslinked polyvinyl chloride of prior art dimercapto-triaizine compounds, adopting the electric wire polymerization degree commonly used is that 950～1050 PVC makes base-material, stearyl alcohol or polyoxyethylene glycol are made catalyzer.Exist rate of crosslinking slower, need crosslinkedly through 15 minutes, and degree of crosslinking has only about 65% the end of than, and performance improves still can not satisfy high request.Therefore still having is worth improved place.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, and the polyvinyl chloride cross linking through sulfhydryl compound that a kind of rate of crosslinking is fast, degree of crosslinking is high is provided.
The object of the invention realizes, the main improvement is in the crosslinked polyvinyl chloride of dimercapto-triaizine compounds, adopt stearyl alcohol and thiazolium compounds as composite catalyst, and polyvinyl chloride resin adopts the polymerization degree 950～1050PVC resin of 60-80 part, with the polymerization degree of 20-40 part be 2450～2550PVC mixed with resin polyvinyl chloride resin, thereby overcome the deficiencies in the prior art, realized the object of the invention.Specifically, polyvinyl chloride cross linking through sulfhydryl compound of the present invention is characterized in that comprising 100 parts of polyvinyl chloride resins, 40～90 parts of softening agent, and 2～6 parts of acid absorbers, 3～7 parts of dimercapto-triaizine compounds linking agents, 0.2～2 part of composite catalyst mixes sulfuration; Described polyvinyl chloride resin is by the polyvinyl chloride resin of the 60-80wt% polymerization degree 950～1050, is that 2450～2550 polyvinyl chloride resin mixes composition with 20～40wt% polymerization degree; Described composite catalyst is mixed with the 20-40wt% thiazolium compounds by 60～80wt% stearyl alcohol and forms.
Polyvinyl chloride cross linking through sulfhydryl compound of the present invention a kind ofly better respectively consists of: 100 parts of polyvinyl chloride resins, and 60～80 parts of softening agent, 2～6 parts of acid absorbers, 3～7 parts of dimercapto-triaizine compounds linking agents, 0.2～2 part of composite catalyst mixes sulfuration; Described polyvinyl chloride resin is by the polyvinyl chloride resin of 60～70wt% polymerization degree 950～1050, is that 2450～2550 polyvinyl chloride resin mixes composition with the 30-40wt% polymerization degree; Described composite catalyst is mixed with 30～40wt% thiazolium compounds by 60～70wt% stearyl alcohol and forms.
Among the present invention
Softening agent is PVC plastics common plasticizers, and for example using always has o-phthalic acid dibutyl ester (DOP), trimellitic acid three hot fat (TOTM), terephthalic acid dibutyl ester (DOTP) etc.Consumption is identical with dimercapto-triaizine compounds crosslinked PVC in the present invention.
Acid absorber is the crosslinked generic acid absorption agents of PVC plastics, and for example using always has magnesium oxide (MgO), plumbous oxide (PbO) and dibasic lead phosphite, lead sulfate tribasic etc.Consumption is identical with dimercapto-triaizine compounds crosslinked PVC in the present invention.
Dimercapto-triaizine compounds linking agent, also same as the prior art, for example using always has 6 dibutylamine 1.3.5 triazine 2.4 2 mercaptan (DB), 2,4,6 tri-thiols, 1,3,5 triazines (TCY).Consumption is identical with dimercapto-triaizine compounds crosslinked PVC in the present invention.
The polyvinyl chloride resin base-material, the employing polymerization degree is respectively 950～1050 (trade mark SG-5) and two kinds of 2450～2550 (trade mark S-200) are compound, mainly is to improve the PVC characteristic that both use with and have taken into account mechanical property and processing performance, make performance obtain complementation, this is the present invention's one big characteristic.More former single employing SG-5 resin, it is good not only to have processing fluidity, the characteristics that extruded velocity is fast, and S-200 resin because of adding a certain amount of high-polymerization degree, macromolecule, long molecular chain, strengthened the intensity of cross-linked resin, intensity can be more former single with SG-5 resin raising 20%, and reduced distortion, and rebound resilience and low temperature flexibility might as well.
Composite catalyst, its effect rises identical with the prior art crosslinking catalyst, the present invention adopts stearyl alcohol and thiazolium compounds to make mixed catalyst, it is the another difference that is different from prior art of the present invention, test shows that mixed catalyst can significantly increase the degree of crosslinking after crosslinked, and degree of crosslinking can bring up to 85% by original 65%, and the sulfuration of gained crosslinked products evenly, improve tensile strength, improved rebound resilience; Secondly, can also improve rate of crosslinking, make to reduce to 8 minutes by original 15 minutes.Thiazolium compounds for example is preferably dibenzothiazyl disulfide (DM), 2-benzothiazolyl mercaptan (M), 2-zinc salt of 2 mercaptobenzothiazole (MZ).
In addition, cross-linked resin of the present invention can also add some admixtures as required, to realize corresponding function.The general weighting agent of PVC that for example can add 20～40 parts, heavy or ground calcium carbonate for example, calcinated argils etc. are to reduce cost; Add the lubricant of amount usually, for example paraffin, stearic acid, Ployethylene Wax etc. are processed extrusion performance to improve; Can also add other functional additives,, realize corresponding function respectively as tinting material, anti-aging agent, anti ultraviolet agent etc.Add-on and prior art are basic identical, not special the variation.
Cross-linking method of the present invention and crosslinked condition, crosslinked also identical with prior art dimercapto-triaizine compounds, have no special requirements.
Polyvinyl chloride cross linking through sulfhydryl compound of the present invention adopts composite polrvinyl chloride and composite catalyst owing to improve, and have than the crosslinked polyvinyl chloride of prior art dimercapto-triaizine compounds: vulcanization rate is fast, and curing time was reduced to 8 minutes from original 15 minutes; The degree of crosslinking height, degree of crosslinking brings up to 85% by original 65%; The physical and mechanical properties excellence, tensile strength is brought up to 20Mpa by original 16Mpa; Rebound resilience and low temperature flexibility also are improved, and these all constitute the difference of cross-linked resin of the present invention and prior art cross-linked resin.Particularly, the crosslinked polyvinyl chloride of gained of the present invention, the degree of crosslinking height, can reach about 85%, apparently higher than the various cross-linking method products obtained therefroms of prior art, for the present invention is different from other crosslinked remarkable distinguishing characteristicss, in crosslinked, there is the polyvinyl chloride resin of two kinds of different polymerization degrees simultaneously simultaneously, also be the another difference that the crosslinked polyvinyl chloride of gained of the present invention is different from the crosslinked polyvinyl chloride of prior art gained.
Below in conjunction with three specific embodiments; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the technical scheme qualification total to the present invention, some do not depart from the unsubstantiality of the present invention's design and change In the view of the technician; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment
Embodiment: referring to subordinate list, polyvinyl chloride resin with two kinds of different polymerization degrees mixes earlier, add acid absorber MgO or PbO, dimercapto-triaizine compounds linking agent DB or TCY, two kinds of catalyzer (stearyl alcohol and DM or M or MZ), tinting material, lubricant polyethylene is cured, mixes dispersion for example 10 seconds in high-speed mixer; Add plasticizer DOP or TOTM again, stir plasticising is absorbed fully by resin, for example be warming up to 50～55 ℃, add weighting agent lime carbonate at last and be stirred to fully and be uniformly dispersed, for example be warming up to 95 ℃; Put into the forcing machine granulation at last.After extruding cable, steam-pipe endless vulcanization that can be by 150-160 ℃ 10 minutes also can be 150-160 ℃ of steam kettle cure 10 minutes.Specific embodiment is basic identical with original sulfuration.
To those skilled in the art; under this patent design and embodiment enlightenment; some distortion that can directly derive or associate from this patent disclosure and general knowledge; or the substituting of known technology commonly used in the prior art; and the mutual various combination between feature; the for example change of compounding ingredient commonly used; blending means changes; or the like unsubstantiality change; can be employed equally; can both realize and basic identical function of the foregoing description and effect, launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
Example formulations (unit: kg) and the salient features table
Claims (6)
1, polyvinyl chloride cross linking through sulfhydryl compound is characterized in that comprising 100 parts of polyvinyl chloride resins, 40～90 parts of softening agent, and 2～6 parts of acid absorbers, 3～7 parts of dimercapto-triaizine compounds linking agents, 0.2～2 part of composite catalyst mixes sulfuration; Described polyvinyl chloride resin is by the polyvinyl chloride resin of the 60-80wt% polymerization degree 950～1050, is that 2450～2550 polyvinyl chloride resin mixes composition with 20～40wt% polymerization degree; Described composite catalyst is mixed with the 20-40wt% thiazolium compounds by 60～80wt% stearyl alcohol and forms.
2, according to the described polyvinyl chloride cross linking through sulfhydryl compound of claim 1, it is characterized in that comprising 100 parts of polyvinyl chloride resins, 60～80 parts of softening agent, 2～6 parts of acid absorbers, 3～7 parts of dimercapto-triaizine compounds linking agents, 0.2～2 part of composite catalyst mixes sulfuration; Described polyvinyl chloride resin is by the polyvinyl chloride resin of 60～70wt% polymerization degree 950～1050, is that 2450～2550 polyvinyl chloride resin mixes composition with the 30-40wt% polymerization degree; Described composite catalyst is mixed with 30～40wt% thiazolium compounds by 60～70wt% stearyl alcohol and forms.
3, according to the described polyvinyl chloride cross linking through sulfhydryl compound of claim 1, it is characterized in that thiazolium compounds is a dibenzothiazyl disulfide, or 2-benzothiazolyl mercaptan, or 2-zinc salt of 2 mercaptobenzothiazole.
4, according to claim 1,2 or 3 described polyvinyl chloride cross linking through sulfhydryl compound, it is characterized in that also comprising 20～40 parts weighting agent.
5,, it is characterized in that also comprising the lubricant of common amount according to the described polyvinyl chloride cross linking through sulfhydryl compound of claim 4.
6,, it is characterized in that also comprising the lubricant of common amount according to claim 1,2 or 3 described polyvinyl chloride cross linking through sulfhydryl compound.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810242855XA CN101445634B (en) | 2008-12-25 | 2008-12-25 | Polyvinyl chloride cross linking method through sulfhydryl compound |
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| CN200810242855XA CN101445634B (en) | 2008-12-25 | 2008-12-25 | Polyvinyl chloride cross linking method through sulfhydryl compound |
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| CN101445634A true CN101445634A (en) | 2009-06-03 |
| CN101445634B CN101445634B (en) | 2010-12-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106448846A (en) * | 2016-12-12 | 2017-02-22 | 广州凯恒特种电线电缆有限公司 | Fluoropolymer wire and cable and preparation thereof |
| CN111253698A (en) * | 2020-04-07 | 2020-06-09 | 安徽弘宜新材料科技发展有限公司 | Multifunctional PVC (polyvinyl chloride) crosslinked cable sheath material and processing technology thereof |
| CN111269508A (en) * | 2020-04-02 | 2020-06-12 | 云南鑫成鹏高分子科技有限公司 | Micro-crosslinked temperature-resistant polyvinyl chloride cable base material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2330353A (en) * | 1940-06-20 | 1943-09-28 | Goodrich Co B F | Mixture of polymerized materials |
| NL105044C (en) * | 1956-12-14 | |||
| US3036980A (en) * | 1956-12-31 | 1962-05-29 | Union Carbide Corp | Rubber composition containing zeolitic molecular sieve and process for curing |
| EP1669397A1 (en) * | 2004-12-01 | 2006-06-14 | Arkema | Stabilizing compositions for chlorine-containing polymers and resins |
| DE602005018254D1 (en) * | 2004-12-16 | 2010-01-21 | Basf Se | STABILIZED FILLER-BASED MATERIALS |
| DE102005055793A1 (en) * | 2005-11-21 | 2007-05-24 | Röhm Gmbh | Transparent TPU (thermoplastic polyurethanes) / PMMA (polymethyl (meth) acrylate) Blends with improved impact resistance |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106448846A (en) * | 2016-12-12 | 2017-02-22 | 广州凯恒特种电线电缆有限公司 | Fluoropolymer wire and cable and preparation thereof |
| CN111269508A (en) * | 2020-04-02 | 2020-06-12 | 云南鑫成鹏高分子科技有限公司 | Micro-crosslinked temperature-resistant polyvinyl chloride cable base material and preparation method thereof |
| CN111253698A (en) * | 2020-04-07 | 2020-06-09 | 安徽弘宜新材料科技发展有限公司 | Multifunctional PVC (polyvinyl chloride) crosslinked cable sheath material and processing technology thereof |
| CN111253698B (en) * | 2020-04-07 | 2022-06-03 | 安徽弘宜新材料科技发展有限公司 | Multifunctional PVC (polyvinyl chloride) crosslinked cable sheath material and processing technology thereof |
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| CN101445634B (en) | 2010-12-08 |
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Granted publication date: 20101208 Termination date: 20161225 |