CN104130527A - High-toughness PVC drainage-pipe material, and preparation method and application thereof - Google Patents
High-toughness PVC drainage-pipe material, and preparation method and application thereof Download PDFInfo
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- CN104130527A CN104130527A CN201410373058.0A CN201410373058A CN104130527A CN 104130527 A CN104130527 A CN 104130527A CN 201410373058 A CN201410373058 A CN 201410373058A CN 104130527 A CN104130527 A CN 104130527A
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Abstract
The invention relates to a high-toughness PVC drainage-pipe material, and a preparation method and application thereof. The PVC drainage-pipe material is prepared according to the following preparation method: taking nanometer calcium carbonate and chlorinated polyethylene as raw materials to prepare a compound modified particle with a core-shell structure through an emulsion polymerization method; and blending the compound modified particle with PVC through melting, so as to prepare a ternary nanometer compound material. By selecting a specific nanometer particle to organically combine with an elastomer, the core-shell structural compound modified particle taking nanometer calcium carbonate as a core and CPE as a shell, then the compound modified particle and PVC resin are subjected to melt blending, so that the compound modified particles are well dispersed in PVC matrix, and give play to toughening reinforcing modification effect on PVC.
Description
Technical field
The present invention relates to plastic pipe technical field, relate in particular to a kind of high tenacity PVC water shoot material and its preparation method and application.
Background technology
In PVC-U water shoot, raw materials used polyvinyl chloride (PVC) is the general-purpose plastics kind of high comprehensive performance, cheap and starting material wide material sources, and its output and consumption are only second to polyethylene, in every field, obtain a wide range of applications.But PVC also exists defect or the deficiency of some performances, wherein fragility is one of disadvantage of PVC plastics.Hard PVC is poor toughness at normal temperatures, and shock strength is low, and toughness is poorer at low temperatures, and while reducing temperature, rapid hardening becomes fragile, very easily embrittlement while being hit, and this has just limited PVC material as the application of structured material and the application in low temperature environment.Therefore, the low-temperature flexibility of improvement PVC has Important Economic and social effect.
Summary of the invention
The object of the present invention is to provide a kind of high tenacity PVC water shoot material, by selecting nano-calcium carbonate and chlorinatedpolyethylene to organically combine, the composite modified particle of nucleocapsid structure that silicon-dioxide is shell as core, the chlorinatedpolyethylene of take is take in formation, and adopt this composite modified particle to carry out modification to PVC, thereby realize, PVC is carried out to tough-increased and reinforced modification.
Another object of the present invention is to provide the preparation method of above-mentioned pvc pipe material.
Another object of the present invention is to provide the application of above-mentioned pvc pipe material in preparation PVC water shoot.
Another object of the present invention is to provide above-mentioned pvc pipe material to prepare the PVC water shoot of gained.
For achieving the above object, the present invention is achieved by following technical solution:
A high tenacity PVC water shoot material, described PVC water shoot material makes by being prepared as follows method:
By emulsion polymerization, take nano-calcium carbonate and chlorinatedpolyethylene and there is the composite modified particle of nucleocapsid structure as raw material preparation; Then by described composite modified particle and PVC melt blending, prepare ternary nano composite material;
Wherein, the quality proportioning of described nano-calcium carbonate and chlorinatedpolyethylene is 10: 1～4; The quality proportioning of described composite modified particle and PVC is 4～6:100.
The present invention is by selecting nano-calcium carbonate and CPE to organically combine, the composite modified particle of nucleocapsid structure that nano-calcium carbonate is shell as core, the CPE of take is take in formation, then by composite modified particle and PVC melt blending, make composite modified particle good distribution in PVC matrix of nucleocapsid structure, and then PVC is carried out to tough-increased and reinforced modification.
Preferably, first described nano-calcium carbonate prepares composite modified particle with chlorinatedpolyethylene again after organic modifiers modification.
After nano-calcium carbonate being processed by organic modifiers, improved dispersiveness and the strengthening and toughening effect of nano-calcium carbonate in compound, change physics, the chemical property of powder surface simultaneously, reduced the reunion of nano-calcium carbonate, this is conducive to fully mixing of nano-calcium carbonate and chlorinatedpolyethylene in subsequent step.
Preferably, nano-calcium carbonate through the concrete operation method of organic modifiers modification is: nano-calcium carbonate and organic modifiers are stirred in 30～120 ℃; Then be heated to 50～120 ℃ and continue solid phase and stir 0～10min; Coolingly obtain composite modified particle.
Further preferably, described organic modifiers is titanate coupling agent NDZ 1, and the consumption of the organic modifiers in the present invention can be with reference to conventional amount used of the prior art.
Preferably, the quality proportioning of nano-calcium carbonate and chlorinatedpolyethylene described in step S1 is 10:3.
Preferably, the quality proportioning of composite modified particle and PVC described in step S3 is 5: 100.
Emulsion polymerization provided by the invention specifically comprises the steps:
Take the reactor that nano-calcium carbonate is placed in condensing works in right amount, add appropriate amount of deionized water, stir, then add emulsifying agent, CPE, also dispersed with stirring is even to be heated to 80～95 ℃, adds initiator, at 80～95 ℃ of thermotonus 2～5h, continue to stir, after reaction finishes, be cooled to room temperature, obtain take nano-calcium carbonate and take the composite modified particle that CPE is shell as core.
Compared with prior art, the present invention designs by morphology of particles, forms and take nano-calcium carbonate as the nucleocapsid structure particle that core, the CPE of take are shell, and PVC is carried out to toughness reinforcing enhancing.Composite modified particle has the advantage of nano-calcium carbonate and CPE toughening PVC concurrently, compares with simple nano-calcium carbonate toughening PVC, because shell is CPE, therefore better with the consistency of PVC; Compare with the trielement composite material that simple nano-calcium carbonate, CPE, PVC blend form; after having formed composite modified particle, be used further to the toughness reinforcing of PVC; more be conducive to composite modified dispersion of particles; therefore adopt the low temperature resistant toughness of the PVC water shoot material of composite modified particle of the present invention to obtain significant enhancing; the present invention, in the original valuable performance of protection PVC, has improved the toughness of PVC water shoot material effectively.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, in embodiment, related reagent, method is the conventional reagent in this area and method.
embodiment 1
Use 100 weight part nano-calcium carbonates and 6 weight part titanate coupling agent NDZ 1 to stir at 30 ℃, obtain mixture standby, the mixture obtaining is heated to 50 ℃ and carry out solid phase and stir 1min, is then cooled to normal temperature to obtain modified nano calcium carbonate, the CPE of the modified nano calcium carbonate of 100 weight parts and 10 weight parts is adopted to emulsion polymerization, prepare to form and take nano-calcium carbonate as core, the composite modified particle concrete operation step of nucleocapsid structure that the CPE of take is shell is the reactor that above-mentioned nano-calcium carbonate after modification is placed in to condensing works, add deionized water, stir, then add emulsifying agent, CPE, also dispersed with stirring is even to be heated to 80 ℃, add normal starter, at 80 ℃ of thermotonus 2h, continue to stir, after finishing, reaction is cooled to room temperature, obtain take nano-calcium carbonate and take the composite modified particle that CPE is shell as core.
Then by the composite modified particle of 4 weight part and 100 weight part PVC melt blendings, make composite modified particle good distribution in PVC matrix, thereby prepare high performance ternary nano composite material.
Above-mentioned high performance ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to the PVC drainage pipe with efficient high tenacity through cooling and shaping.
embodiment 2
Use 100 weight part nano-calcium carbonates and 8 weight part titanate coupling agent NDZ 1 to stir at 50 ℃, obtain mixture standby, the mixture obtaining is heated to 70 ℃ and carry out solid phase and stir 4min, is then cooled to normal temperature to obtain modified nano calcium carbonate, the CPE of the modified nano calcium carbonate of 100 weight parts and 15 weight parts is adopted to emulsion polymerization, prepare to form and take nano-calcium carbonate as core, the composite modified particle of nucleocapsid structure that the CPE of take is shell, concrete operation step is: the reactor that above-mentioned nano-calcium carbonate after modification is placed in to condensing works, add deionized water, stir, then add emulsifying agent, CPE, also dispersed with stirring is even to be heated to 85 ℃, add normal starter, at 85 ℃ of thermotonus 3h, continue to stir, after finishing, reaction is cooled to room temperature, obtain take nano-calcium carbonate and take the composite modified particle that CPE is shell as core.
Then by the composite modified particle of 5 weight part and 100 weight part PVC melt blendings, make composite modified particle good distribution in PVC matrix, thereby prepare high performance ternary nano composite material.
Above-mentioned high performance ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to the PVC drainage pipe with efficient high tenacity through cooling and shaping.
embodiment 3
Use 100 weight part nano-calcium carbonates and 10 weight part titanate coupling agent NDZ 1 to stir at 100 ℃, obtain mixture standby, the mixture obtaining is heated to 100 ℃ and carry out solid phase and stir 8min, is then cooled to normal temperature to obtain modified nano calcium carbonate, the CPE of the modified nano calcium carbonate of 100 weight parts and 20 weight parts is adopted to emulsion polymerization, prepare to form and take nano-calcium carbonate as core, the composite modified particle of nucleocapsid structure that the CPE of take is shell, concrete operation step is: the reactor that above-mentioned nano-calcium carbonate after modification is placed in to condensing works, add deionized water, stir, then add emulsifying agent, CPE, also dispersed with stirring is even to be heated to 90 ℃, add normal starter, at 90 ℃ of thermotonus 3h, continue to stir, after finishing, reaction is cooled to room temperature, obtain take nano-calcium carbonate and take the composite modified particle that CPE is shell as core.
Then by the composite modified particle of 6 weight part and 100 weight part PVC melt blendings, make composite modified particle good distribution in PVC matrix, thereby prepare high performance ternary nano composite material.
Above-mentioned high performance ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to the PVC drainage pipe with efficient high tenacity through cooling and shaping.
embodiment 4
Use 100 weight part nano-calcium carbonates and 12 weight part titanate coupling agent NDZ 1 to stir at 120 ℃, obtain mixture standby, the mixture obtaining is heated to 120 ℃ and carry out solid phase and stir 10min, is then cooled to normal temperature to obtain modified nano calcium carbonate, the CPE of the modified nano calcium carbonate of 100 weight parts and 30 weight parts is adopted to emulsion polymerization, prepare to form and take nano-calcium carbonate as core, the composite modified particle of nucleocapsid structure that the CPE of take is shell, concrete operation step is: the reactor that above-mentioned nano-calcium carbonate after modification is placed in to condensing works, add deionized water, stir, then add emulsifying agent, CPE, also dispersed with stirring is even to be heated to 95 ℃, add normal starter, at 95 ℃ of thermotonus 4h, continue to stir, after finishing, reaction is cooled to room temperature, obtain take nano-calcium carbonate and take the composite modified particle that CPE is shell as core.
Then by the composite modified particle of 6 weight part and 100 weight part PVC melt blendings, make composite modified particle good distribution in PVC matrix, thereby prepare high performance ternary nano composite material.
Above-mentioned high performance ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to the PVC drainage pipe with efficient high tenacity through cooling and shaping.
embodiment 5
Use 100 weight part nano-calcium carbonates and 15 weight part titanate coupling agent NDZ 1 to stir at 100 ℃, obtain mixture standby, the mixture obtaining is heated to 100 ℃ and carry out solid phase and stir 10min, is then cooled to normal temperature to obtain modified nano calcium carbonate, the CPE of the modified nano calcium carbonate of 100 weight parts and 40 weight parts is adopted to emulsion polymerization, prepare to form and take nano-calcium carbonate as core, the composite modified particle of nucleocapsid structure that the CPE of take is shell, concrete operation step is: the reactor that above-mentioned nano-calcium carbonate after modification is placed in to condensing works, add deionized water, stir, then add emulsifying agent, CPE, also dispersed with stirring is even to be heated to 90 ℃, add normal starter, at 90 ℃ of thermotonus 5h, continue to stir, after finishing, reaction is cooled to room temperature, obtain take nano-calcium carbonate and take the composite modified particle that CPE is shell as core.
Then by the composite modified particle of 5 weight part and 100 weight part PVC melt blendings, make composite modified particle good distribution in PVC matrix, thereby prepare high performance ternary nano composite material.
Above-mentioned high performance ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to the PVC drainage pipe with efficient high tenacity through cooling and shaping.
comparative example 1
Use the CPE blend of titanate coupling agent NDZ mono-101,10 weight parts of 100 weight part nano-calcium carbonates, 6 weight parts to form mixture, standby; By the said mixture of 5 weight parts and 100 weight part PVC melt blendings, prepare high performance ternary nano composite material;
Above-mentioned ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to PVC drainage pipe through cooling and shaping.
comparative example 2
Use 100 weight part nano-calcium carbonates and 10 weight part titanate coupling agent NDZ 1 to stir at 100 ℃, obtain mixture standby, the mixture obtaining is heated to 100 ℃ and carry out solid phase and stir 8min, is then cooled to normal temperature to obtain modified nano calcium carbonate, the ABS of the modified nano calcium carbonate of 100 weight parts and 20 weight parts is adopted to emulsion polymerization, prepare to form and take nano-calcium carbonate as core, the composite modified particle of nucleocapsid structure that the ABS of take is shell, concrete operation step is: the reactor that above-mentioned nano-calcium carbonate after modification is placed in to condensing works, add deionized water, stir, then add emulsifying agent, ABS, also dispersed with stirring is even to be heated to 95 ℃, add normal starter, at 95 ℃ of thermotonus 5h, continue to stir, after finishing, reaction is cooled to room temperature, obtain take nano-calcium carbonate and take the composite modified particle that ABS is shell as core.
Then by the composite modified particle of 5 weight part and 100 weight part PVC melt blendings, make composite modified particle good distribution in PVC matrix, thereby prepare high performance ternary nano composite material.
Above-mentioned high performance ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to the PVC drainage pipe with efficient high tenacity through cooling and shaping.
comparative example 3
Use 100 weight part nano silicons and 15 weight part titanate coupling agent NDZ 1 to stir at 100 ℃, obtain mixture standby, the mixture obtaining is heated to 100 ℃ and carry out solid phase and stir 10min, is then cooled to normal temperature to obtain modified manometer silicon dioxide, the CPE of the modified manometer silicon dioxide of 100 weight parts and 40 weight parts is adopted to emulsion polymerization, prepare to form and take nano silicon as core, the composite modified particle of nucleocapsid structure that the CPE of take is shell, concrete operation step is: the reactor that above-mentioned nano silicon after modification is placed in to condensing works, add deionized water, stir, then add emulsifying agent, CPE, also dispersed with stirring is even to be heated to 85 ℃, add normal starter, at 85 ℃ of thermotonus 3h, continue to stir, after finishing, reaction is cooled to room temperature, obtain take nano silicon and take the composite modified particle that CPE is shell as core.
Then by the composite modified particle of 5 weight part and 100 weight part PVC melt blendings, make composite modified particle good distribution in PVC matrix, thereby prepare high performance ternary nano composite material.
Above-mentioned high performance ternary nano composite material, through twin screw extruder melt blending and moulding, then is made to the PVC drainage pipe with efficient high tenacity through cooling and shaping.
The PVC drainage pipe that embodiment 1～5 and comparative example 1～3 are prepared to gained carries out toughness test, and test result sees the following form 1.
The pvc pipe mechanical property preparing in various embodiments of the present invention and comparative example is measured according to following measuring method:
Tensile strength, tests by GB/T8804.2-2003 standard;
Elongation at break, tests by GB/T5836-1996 standard;
Low temperature impact strength, tests by GB/T13525-1992 standard;
Normal temperature shock strength, tests by GB/T13525-1992 standard.
Table 1
。
As shown in Table 1, the present invention has high tenacity by the preparation-obtained PVC water shoot of emulsion polymerization, toughness under-18 ℃ of conditions is still greater than 10KJ/ ㎡, the present invention simultaneously has higher tensile strength, elongation at break and shock strength, there is good physical strength, can be applied to various occasions.
Claims (9)
1. a high tenacity PVC water shoot material, is characterized in that, described PVC water shoot material makes by being prepared as follows method:
By emulsion polymerization, take nano-calcium carbonate and chlorinatedpolyethylene and there is the composite modified particle of nucleocapsid structure as raw material preparation; Then by described composite modified particle and PVC melt blending, prepare ternary nano composite material;
Wherein, the quality proportioning of described nano-calcium carbonate and chlorinatedpolyethylene is 10: 1～4; The quality proportioning of described composite modified particle and PVC is 4～6:100.
2. high tenacity PVC water shoot material according to claim 1, is characterized in that, first described nano-calcium carbonate prepares composite modified particle with chlorinatedpolyethylene again after organic modifiers modification.
3. high tenacity PVC water shoot material according to claim 2, is characterized in that, nano-calcium carbonate through the working method of organic modifiers modification is: nano-calcium carbonate and organic modifiers are stirred in 30～120 ℃; Then be heated to 50～120 ℃ and continue solid phase and stir 0～10min; Coolingly obtain composite modified particle.
4. high tenacity PVC water shoot material according to claim 1, is characterized in that, described organic modifiers is titanate coupling agent.
5. high tenacity PVC water shoot material according to claim 1, is characterized in that, the quality proportioning of described nano-calcium carbonate and chlorinatedpolyethylene is 10:3.
6. high tenacity PVC water shoot material according to claim 1, is characterized in that, the quality proportioning of described composite modified particle and PVC is 5: 100.
7. the preparation method of the high tenacity PVC water shoot material described in the arbitrary claim of claim 1～6, is characterized in that, described emulsion polymerization comprises the steps:
S1: take the reactor that nano-calcium carbonate is placed in condensing works, add deionized water, stir;
S2: add emulsifying agent, chlorinatedpolyethylene in above-mentioned mixed solution, also dispersed with stirring is even to be heated to 80～95 ℃, obtains mixed solution standby;
S3: add initiator in the mixed solution of step S2, at 80～95 ℃ of thermotonus 2～5h, continue to stir, reaction finishes rear cooling, obtains take nano-calcium carbonate and take the composite modified particle that chlorinatedpolyethylene is shell as core.
8. the application of the high tenacity PVC water shoot material described in the arbitrary claim of claim 1～6 in preparation PVC water shoot.
9. the high tenacity PVC water shoot material described in the arbitrary claim of claim 1～6 is prepared the PVC water shoot of gained.
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| WO2017222483A1 (en) * | 2016-06-23 | 2017-12-28 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | A cost-effective impact resistance-increasing hybrid composite material and a production method thereof |
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| CN104130527B (en) | 2016-08-24 |
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