CN101768325A - Application of linear phenolic resin in serving as stable modifying agent - Google Patents
Application of linear phenolic resin in serving as stable modifying agent Download PDFInfo
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- CN101768325A CN101768325A CN201010101320A CN201010101320A CN101768325A CN 101768325 A CN101768325 A CN 101768325A CN 201010101320 A CN201010101320 A CN 201010101320A CN 201010101320 A CN201010101320 A CN 201010101320A CN 101768325 A CN101768325 A CN 101768325A
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Abstract
The invention discloses application of a linear phenolic resin in serving as a stable modifying agent. The linear phenolic resin is prepared by performing condensation polymerization on a phenolic compound, an aldehyde compound and/or a vinyl compound. The average molecular weight of the linear phenolic resin is between 300 and 10,000. The linear phenolic resin can be applied to calcium-zinc and rare earth stabilizing agents, and also can be directly applied to halogen-containing polymers. The linear phenolic resin serving as the stable modifying agent can significantly improve the processing stability and the electric insulating property of the halogen-containing polymers.
Description
Technical field
The present invention relates to chemical field, specifically, relate to a kind of thermo-stabilizer properties-correcting agent of polymer containing halogen.
Background technology
Polymer containing halogen for example polyvinyl chloride etc. has superior corrosion resistance and mechanical property, cheap simultaneously, abundant raw material, manufacturing process maturation, and its goods are widely used in the every field of industrial and agricultural production.Yet polymer containing halogen adds that a fatal weakness is arranged man-hour is poor heat stability.It mainly can be divided into lead stabilizer, calcium zinc stabilizer, organotin stabilizer, rare-earth stabilizer etc. by chemical constitution the thermo-stabilizer that polymer containing halogen is used always.
Lead salt stabilizer is an also thermo-stabilizer preferably of the longest and effect of applicating history, is extensive use of in PVC section bar, tubing, insulated cable material.Alkali formula lead salt is present most widely used lead stabilizer.The lead stabilizer thermotolerance is good, and particularly long-term thermal stability is good; Electric insulating quality is good; Have the performance of white pigment, hiding power is big, and weathering resistance is also good; Can make the promoting agent of whipping agent and cheap.But lead stabilizer also has many shortcomings: resulting product is opaque; Toxicity is big; Initial coloring is arranged; Consistency and bad dispersibility are easy to generate sulfide staining.
Organo-tin compound is a thermo-stabilizer efficiently, is specially adapted to require the boardy product of heigh clarity and highly heat-resistant.They often play the function of photochemistry, power chemistry and biological chemistry stablizer, softening agent etc., are widely used and replace other thermo-stabilizers.But its price is higher, has limited their application to a certain extent, simultaneously, in Europe the stanniferous amount in the plastics is strictly limited (permission content is 0.002mg/kg), has further limited the application of organotin stabilizer.
Calcium zinc stabilizer and rare-earth stabilizer are that a class is nontoxic and have the environmental protection thermo-stabilizer of good lubrication, but its thermostability is not high, and for a long time thermostabilitys that are used for require not too high PVC soft goods or use as auxiliary heat stabilizer once in a while more.In recent years, along with the exploitation of organic auxiliary addition agent such as-diketone, polyvalent alcohol, epoxy compounds etc., Ca-Zn composite heat stabilizer has also obtained very big development.But calcium zinc stabilizer and rare-earth stabilizer thermal stability are low and insulating property are poor, seriously restrict further developing of they.
Summary of the invention
Purpose of the present invention overcomes existing nontoxic calcium zinc one package stabilizer and the rare-earth stabilizer thermal stability is low, the shortcoming of goods insulating property difference, and a kind of new stable modification agent linear phenolic resin is provided.This linear phenolic resin stable modification agent can significantly improve the heat-stable time of goods, significantly delays the xanthochromia time and the insulating property that significantly improve goods of goods.
To achieve these goals, the present invention adopts following technical scheme:
The present invention finds that through a large amount of experimental studies linear phenolic resin can be used for the stable modification agent as polymer containing halogen as the stable modification agent.
When adding linear phenolic resin in the polymer containing halogen, its addition is preferably the 0.005-2.0% of polymer containing halogen weight resin.
Polymer containing halogen of the present invention can be chlorinatedpolyethylene, chlorinated natural rubber, Benzene Chloride ethene, chlorinated polyvinyl chloride or the vinyl chloride-base polymer that contains 14-75% (weight part) chlorine.Described vinyl chloride-base polymer can be made up of separately vinylchlorid, but the multipolymer that also can make by the vinyl monomer of the vinyl chloride monomer that accounts for monomer 70% weight at least and copolymerization.Described vinyl monomer comprises vinyl acetate, vinyl butyrate, vinyl benzoate, toxilic acid second diester etc.
The preferred molecular-weight average of linear phenolic resin is between 300-10000.
Above-mentioned linear phenolic resin is formed by phenolic compound, both polycondensations of aldehyde compound or phenolic compound, aldehyde compound, vinyl compound three polycondensation.
Described phenolic compound is preferably one or more mixing in phenol, naphthols, mono-substituted phenol, catechol, quinhydrones, dihydroxyphenyl propane, Bisphenol F, the naphthols.
It is one or more mixing in formaldehyde, Paraformaldehyde 96, phenyl aldehyde, phenylacetic aldehyde, furfural, the naphthaldehyde that described aldehyde compound is preferably aldehyde.
Described vinyl compound is preferably ethene, propylene, butylene, vinylbenzene, a-vinyl toluene, vinyl ether, acrylate, methacrylic ester, divinyl, with one or more mixing in pentadiene, dicyclopentadiene, the terpenes.
Described linear phenolic resin can mix as the stable modification agent with calcium zinc or rare-earth stabilizer, and its addition is the 0.01-50.0 weight % of calcium zinc or rare-earth stabilizer.
When with described linear phenolic resin during, can also add one or more the additive in thermo-stabilizer, softening agent, pigment, filler, anti-impact modifier, whipping agent, fire retardant, static inhibitor, dyestuff, UV light absorber, oxidation inhibitor, viscosifying agent, the biocide as the stable modification agent of polymer containing halogen.
Linear phenolic resin of the present invention can be purchased on market, or adopts the synthesis technique of linear phenolic resin to be prepared.
The present invention compared with prior art has following advantage and effect.
When (1) linear phenolic resin and calcium zinc or rare-earth stabilizer are shared, can significantly improve the heat-stable time of goods.
(2) linear phenolic resin separately or with calcium zinc (or rare earth) when stablizer is shared, can significantly delay the xanthochromia time of goods.
(3) linear phenolic resin separately or with calcium zinc (or rare earth) when stablizer is shared, can significantly improve the insulating property of goods.
Embodiment
Embodiment 1
PVC 100g, DOP 50g, CaCO
350g, calcium zinc stabilizer 6g, the two roll-in sheets of resol 0.5g are measured the Congo red variable color time (pressing the GB9349-2002 standard test).
The Congo red variable color time/min of table 1
| Sequence number | Resol | Molecular-weight average | Congo red variable color time/min |
| ??1 | Comparative Examples 1 | ??59 | |
| ??2 | P tert butylphenol formaldehyde resin | ??400 | ??64 |
| ??3 | The tert.-butylbenzene fluosite | ??2000 | ??69 |
| ??4 | The p-methyl phenol formaldehyde resin | ??1500 | ??76 |
| Sequence number | Resol | Molecular-weight average | Congo red variable color time/min |
| ??4 | The p-methyl phenol formaldehyde resin | ??10000 | ??71 |
Comparative Examples 1
PVC 100g, DOP 50g, CaCO
3The two roll-in sheets of 50g, calcium zinc stabilizer 6g are measured the Congo red variable color time by the GB9349-2002 standard test), see Table 1.
As can be seen from Table 1, add the Congo red variable color time that 0.5g resol thermal stabilization modifying agent can obviously prolong goods.
Embodiment 2
PVC 100g, TOTM 50g, CaCO
350g, calcium zinc stabilizer 6g, ortho-cresol formaldehyde resin (molecular-weight average 1500) 1g.Be extruded into cable, at 60 degrees centigrade down after soaked 14 days, measure the 14th day and the 1st day relative rate of change of capacitance, measurement result is 4.2.
Comparative Examples 2
PVC 100g, TOTM 50g, CaCO
350g, calcium zinc stabilizer 6g are extruded into cable, at 60 degrees centigrade down after soaked 14 days, measure the 14th day and the 1st day relative rate of change of capacitance, and measurement result is 11.3.
As can be seen from Table 2, behind the interpolation 1g ortho-cresol formaldehyde resin, rate of change of capacitance obviously improves relatively.
Embodiment 3
PVC 100g, CaCO
310g, calcium zinc stabilizer 3g, the end capped p-cresol formaldehyde resin of iso-butylene (molecular-weight average 5000) 0.3g.Carry out 180 degree oven ageings behind two roll-in sheets, measuring the Db value with color difference meter behind the 50min is 20 (the Db value adopts the Coloreye7000 color difference meter to measure, and sample b value is poor before and after its value=oven ageing, and the Db value is big more, and flavescence is obvious more).
Comparative Examples 3
PVC 100g, CaCO
310g, calcium zinc stabilizer 3g.Carry out 180 degree oven ageings behind two roll-in sheets, measuring the Db value with color difference meter behind the 50min is 16.
As can be seen from Table 3, behind the end capped p-cresol formaldehyde resin of the interpolation 0.3g iso-butylene thermal stabilization modifying agent, phase goods xanthochromia is slower.
Embodiment 4
CPVC 50g, CaCO
35g, rare-earth stabilizer 2g, ACR 1.5g, the end capped p-cresol formaldehyde resin of iso-butylene (molecular-weight average 5000) 0.2g.Adopting the Brabender method to measure the dynamic thermal decomposition time of CPVC under 185 ℃ of conditions is 31min.
Comparative Examples 4
CPVC 50g, CaCO
35g, rare-earth stabilizer 2g, ACR 1.5g.Adopting the Brabender method to measure the dynamic thermal decomposition time of CPVC under 185 ℃ of conditions is 28min.
As can be seen from Table 4, behind the end capped p-cresol formaldehyde resin of the interpolation 0.2g iso-butylene thermal stabilization modifying agent, the dynamic heat-stable time of CPVC improves 10%.
Claims (10)
1. linear phenolic resin is as the application in the stable modification agent.
2. application as claimed in claim 1, the molecular-weight average that it is characterized in that described linear phenolic resin is between 300-10000.
3. application as claimed in claim 1 is characterized in that described linear phenolic resin is formed by phenolic compound, both polycondensations of aldehyde compound or phenolic compound, aldehyde compound, vinyl compound three polycondensation.
4. application as claimed in claim 1 is characterized in that described phenolic compound is one or more mixing in phenol, naphthols, mono-substituted phenol, catechol, quinhydrones, dihydroxyphenyl propane, Bisphenol F, the naphthols.
5. application as claimed in claim 1 is characterized in that described aldehyde compound is that aldehyde is one or more mixing in formaldehyde, Paraformaldehyde 96, phenyl aldehyde, phenylacetic aldehyde, furfural, the naphthaldehyde.
6. application as claimed in claim 1, it is characterized in that described vinyl compound be ethene, propylene, butylene, vinylbenzene, a-vinyl toluene, vinyl ether, acrylate, methacrylic ester, divinyl, with one or more mixing in pentadiene, dicyclopentadiene, the terpenes.
7. application as claimed in claim 1 is characterized in that linear phenolic resin is the stable modification agent as polymer containing halogen.
8. application as claimed in claim 8 is characterized in that described linear phenolic resin in polymer containing halogen, and its addition is the 0.005-2.0% of polymer containing halogen weight resin.
9. application as claimed in claim 1 is characterized in that described linear phenolic resin is to mix as the stable modification agent with calcium zinc or rare-earth stabilizer, and its addition is the 0.01-50.0 weight % of calcium zinc or rare-earth stabilizer.
10. application as claimed in claim 1, when it is characterized in that described linear phenolic resin, also be added with one or more the additive in thermo-stabilizer, softening agent, pigment, filler, anti-impact modifier, whipping agent, fire retardant, static inhibitor, dyestuff, UV light absorber, oxidation inhibitor, viscosifying agent, the biocide as the stable modification agent of polymer containing halogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010101320A CN101768325A (en) | 2010-01-22 | 2010-01-22 | Application of linear phenolic resin in serving as stable modifying agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010101320A CN101768325A (en) | 2010-01-22 | 2010-01-22 | Application of linear phenolic resin in serving as stable modifying agent |
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| CN101768325A true CN101768325A (en) | 2010-07-07 |
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| CN201010101320A Pending CN101768325A (en) | 2010-01-22 | 2010-01-22 | Application of linear phenolic resin in serving as stable modifying agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102590029A (en) * | 2011-12-23 | 2012-07-18 | 湖北犇星化工有限责任公司 | Method for determining stability of PVC heat stabilizer |
| CN103289223A (en) * | 2013-02-28 | 2013-09-11 | 章磊 | Novel heat, wear and low temperature resistant PVC pipe |
| CN103571081A (en) * | 2013-09-17 | 2014-02-12 | 申少进 | Composition for preparing rubber rain shoes by utilizing recycled materials |
| CN104017290A (en) * | 2013-02-28 | 2014-09-03 | 章磊 | Novel, heat-resistant, wear-resistant and low-temperature resistant PVC (Polyvinyl Chloride) pipe material |
| CN104017289A (en) * | 2013-02-28 | 2014-09-03 | 章磊 | Novel, heat-resistant, wear-resistant and low-temperature resistant PVC (Polyvinyl Chloride) pipe material |
-
2010
- 2010-01-22 CN CN201010101320A patent/CN101768325A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102590029A (en) * | 2011-12-23 | 2012-07-18 | 湖北犇星化工有限责任公司 | Method for determining stability of PVC heat stabilizer |
| CN103289223A (en) * | 2013-02-28 | 2013-09-11 | 章磊 | Novel heat, wear and low temperature resistant PVC pipe |
| CN104017290A (en) * | 2013-02-28 | 2014-09-03 | 章磊 | Novel, heat-resistant, wear-resistant and low-temperature resistant PVC (Polyvinyl Chloride) pipe material |
| CN104017289A (en) * | 2013-02-28 | 2014-09-03 | 章磊 | Novel, heat-resistant, wear-resistant and low-temperature resistant PVC (Polyvinyl Chloride) pipe material |
| CN103289223B (en) * | 2013-02-28 | 2015-07-08 | 章磊 | Novel heat, wear and low temperature resistant PVC pipe |
| CN103571081A (en) * | 2013-09-17 | 2014-02-12 | 申少进 | Composition for preparing rubber rain shoes by utilizing recycled materials |
| CN103571081B (en) * | 2013-09-17 | 2015-08-05 | 申少进 | A kind of composition utilizing reworked material to prepare rubber rain shoes |
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Application publication date: 20100707 |