CN103483875A - Method for modifying nano calcium carbonate by titanate and preparation method of PVC (polyvinyl chloride) plastic - Google Patents
Method for modifying nano calcium carbonate by titanate and preparation method of PVC (polyvinyl chloride) plastic Download PDFInfo
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- CN103483875A CN103483875A CN201310455849.3A CN201310455849A CN103483875A CN 103483875 A CN103483875 A CN 103483875A CN 201310455849 A CN201310455849 A CN 201310455849A CN 103483875 A CN103483875 A CN 103483875A
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Abstract
The invention discloses a method for modifying nano calcium carbonate by titanate and a preparation method of PVC plastic. The method for modifying nano calcium carbonate by bis (p,p-bis-ethylhexyl diphosphato) ethanediolato titanate comprises the steps as follows: (1), dispersing nano calcium carbonate in deionized water; (2), adding bis (p,p-bis-ethylhexyl diphosphato) ethanediolato titanate, and continuously performing dispersion; and (3), performing filtering and drying. According to the method, bis (p,p-bis-ethylhexyl diphosphato) ethanediolato titanate is adopted for coating nano calcium carbonate dispersed in a liquid phase, so that lipophilicity of nano calcium carbonate is enhanced, dispersibility and liquidity of nano calcium carbonate in PVC resin are improved, and good compatibility between nano calcium carbonate and the PVC resin is obtained; and further, through the improvement of compatibility, stronger cohesion between the PVC resin and nano calcium carbonate is guaranteed, and a mechanical property and a rheological property are improved.
Description
Technical field
The present invention relates to the technical field of PVC, relate in particular to a kind of method of titanic acid ester modified nano calcium carbonate and the preparation method of PVC plastics.
Background technology
The PVC(polyvinyl chloride) be one of general-purpose plastics of high comprehensive performance, there are fire-retardant, corrosion-resistant, insulation, good over-all properties and cheap, the starting material wide material sources such as wear-resistant, be applied widely in every field.But PVC is in processed and applied, during especially as structured material, also exposed the shortcomings such as shock strength is low, poor heat stability, its UV resistant performance is poor in addition, under the sunlight long-term irradiation, is easy to out of doors aging, therefore need to carry out modification to it, improve its application performance.Nano-calcium carbonate is a kind of good mineral filler, in the PVC field, has broad application prospects.But because the specific surface area of nano-calcium carbonate is large, surface can be high, easily reunites; Simultaneously, surface polarity is large, and wetting ability is very strong, and between organic matrix a little less than avidity, easily causes boundary defect, causes material property to descend.Therefore, be necessary calcium carbonate is carried out to surface modification, to reduce its surperficial potential energy, improve hydrophilic oleophobic property, improve its dispersive ability in plastics and with the avidity of organic matrix.
After the prior art modification, the consistency of nano-calcium carbonate and PVC is poor, nanon calcium carbonatefilled after modification is not made after PVC to the mechanical property of PVC, for example tensile strength, elongation at break and shock strength are greatly improved, and rheological property does not obtain larger improvement yet.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of method of titanic acid ester modified nano calcium carbonate, the method can make the consistency of modified nano calcium carbonate and PVC good, adopts PVC plastics prepared by this modified nano calcium carbonate to have excellent mechanical property and rheological property.
A kind of method of Di(dioctylpyrophosphato) ethylene titanate modified nano calcium carbonate comprises the following steps:
(1) nano-calcium carbonate is added in deionized water, under the rotating speed of 2500～4000rpm, stir 5～10min;
(2) account for nano-calcium carbonate quality 0.4～1.4% Di(dioctylpyrophosphato) ethylene titanate to adding in the deionized water that is dispersed with nano-calcium carbonate through stirring, at the temperature of 50～70 ℃, stir 60～120min under the rotating speed of 2500～4000rpm, make calcium carbonate and disperse liquid;
(3) described calcium carbonate is disperseed in liquid to filter and drying, make modified nano calcium carbonate.
Wherein, described step (3) also comprises the modified nano calcium carbonate of drying is ground and sieves afterwards.
Wherein, in described step (1), the median size of nano-calcium carbonate is 30～50nm.
Wherein, in described step (3), the median size of modified nano calcium carbonate is 200～440nm.
In the technical scheme of the method for modifying of above nano-calcium carbonate, selecting Di(dioctylpyrophosphato) ethylene titanate is dispersion agent.Not only contained phosphate-based in its molecular structure but also contained titanate-based, thereby, more only containing titanic acid ester or phosphate-based dispersion agent, its dissemination is stronger.The UP-311 that the Di(dioctylpyrophosphato) ethylene titanate of the technical program is Nanjing You Pu chemical company.Molecular formula is C
34h
74o
16p
4ti, CAS is numbered 65467-75-6, its outward appearance be micro-yellow to the transparent thick liquid of brown color, there is stability preferably in water, facile hydrolysis does not have stronger emulsifying property simultaneously in water.
A kind of method that adopts modified nano calcium carbonate described above to prepare the PVC plastics comprises the following steps:
(1) take the polyvinyl chloride resin quality as benchmark, after the modified nano calcium carbonate by 30～60%, 3～8% lead sulfate tribasic, 2～12% DOP and polyvinyl chloride resin mix, carry out the mixing rubber unvulcanizate that obtains;
(2) rubber unvulcanizate is vulcanized, then cooling forming, make the PVC plastics;
Wherein, mixingly in described step (1) in twin-roll plastic mixing mill, carry out, melting temperature is 170～190 ℃, and mixing time is 8～15min.
Wherein, in described step (2), sulfuration is specially: until after 175～185 ℃ of lower preheating 8～15min, insert in mould and suppress 2～5min one-tenth sheet material under 14～15Mpa.
Wherein, cooling forming is specially in described step (2): the cross-linked rubber obtained after sulfuration is gone on flat-bed press while hot, insert rapidly under the pressure of 14～15Mpa, and cooling under not higher than 60 ℃.
In the preparation scheme of above PVC plastics, DOP is as softening agent.Its Chinese full name is dioctyl phthalate (DOP), is called again synthetic vegetable esters.Compared to softening agent such as ATBC/DOTP, its non-toxic and safe environmental protection.
Select lead sulfate tribasic as thermo-stabilizer.It has good thermotolerance and electrical insulating property, and its light fastness, be particularly suitable for high temperature process.
The present invention adopts Di(dioctylpyrophosphato) ethylene titanate to be coated the nano-calcium carbonate be scattered in liquid phase, strengthen the lipophilicity of nano-calcium carbonate, thereby improved dispersiveness and the mobility of nano-calcium carbonate in polyvinyl chloride resin, made nano-calcium carbonate and polyvinyl chloride resin there is good consistency.The raising of consistency guarantees the stronger bonding force of polyvinyl chloride resin and nano-calcium carbonate, has improved mechanical property and rheological property.
Embodiment
Below the present invention is described in further detail in conjunction with the embodiments respectively.
Embodiment 1
The nano-calcium carbonate that is 30nm by median size adds in the large flask that deionized water is housed, and flask is inserted in thermostat water bath, for flask installs homogenizer, stirring rod is inserted to the correct position below liquid level.Controlling bath temperature is 50 ℃.Start stirrer, the control rotating speed is 2500rpm.Add after stirring 5min and account for nano-calcium carbonate quality 0.4% Di(dioctylpyrophosphato) ethylene titanate, continue to stir 60min, make calcium carbonate and disperse liquid.By the median size of the nanoparticle in the Master2000 type laser particle size analyzer test calcium carbonate dispersion liquid of Britain Ma Erwen company, be 440nm.Then calcium carbonate is disperseed liquid successively filtered, dry, grind and cross 200 mesh sieves and obtain modified nano calcium carbonate.
Take the polyvinyl chloride resin quality as benchmark, and the modified nano calcium carbonate by 30%, 3% lead sulfate tribasic, 2% DOP and polyvinyl chloride resin are transferred in twin-roll plastic mixing mill mixing 8min under 170 ℃ after inserting in high-speed mixer and mixing fully.Then by rubber unvulcanizate after 175 ℃ of lower preheating 8min, insert in mould compacting 2min under 14Mpa and become sheet material.Then, go to while hot on flat-bed press, insert rapidly under the pressure of 14Mpa, cooling under not higher than 60 ℃, make the PVC plastics.
Embodiment 2
The nano-calcium carbonate that is 35nm by median size adds in the large flask that deionized water is housed, and flask is inserted in thermostat water bath, for flask installs homogenizer, stirring rod is inserted to the correct position below liquid level.Controlling bath temperature is 55 ℃.Start stirrer, the control rotating speed is 3000rpm.Add after stirring 7min and account for nano-calcium carbonate quality 0.6% Di(dioctylpyrophosphato) ethylene titanate, continue to stir 80min, make calcium carbonate and disperse liquid.By the median size of the nanoparticle in the Master2000 type laser particle size analyzer test calcium carbonate dispersion liquid of Britain Ma Erwen company, be 405nm.Then calcium carbonate is disperseed liquid successively filtered, dry, grind and cross 200 mesh sieves and obtain modified nano calcium carbonate.
Take the polyvinyl chloride resin quality as benchmark, and the modified nano calcium carbonate by 40%, 4% lead sulfate tribasic, 3% DOP and polyvinyl chloride resin are transferred in twin-roll plastic mixing mill mixing 10min under 175 ℃ after inserting in high-speed mixer and mixing fully.Then by rubber unvulcanizate after 180 ℃ of lower preheating 10min, insert in mould compacting 3min under 14Mpa and become sheet material.Then, go to while hot on flat-bed press, insert rapidly under the pressure of 14Mpa, cooling under not higher than 60 ℃, make the PVC plastics.
Embodiment 3.
The nano-calcium carbonate that is 40nm by median size adds in the large flask that deionized water is housed, and flask is inserted in thermostat water bath, for flask installs homogenizer, stirring rod is inserted to the correct position below liquid level.Controlling bath temperature is 60 ℃.Start stirrer, the control rotating speed is 3500rpm.Add after stirring 8min and account for nano-calcium carbonate quality 0.9% Di(dioctylpyrophosphato) ethylene titanate, continue to stir 90min, make calcium carbonate and disperse liquid.By the median size of the nanoparticle in the Master2000 type laser particle size analyzer test calcium carbonate dispersion liquid of Britain Ma Erwen company, be 340nm.Then calcium carbonate is disperseed liquid successively filtered, dry, grind and cross 200 mesh sieves and obtain modified nano calcium carbonate.
Take the polyvinyl chloride resin quality as benchmark, and the modified nano calcium carbonate by 45%, 6% lead sulfate tribasic, 5% DOP and polyvinyl chloride resin are transferred in twin-roll plastic mixing mill mixing 12min under 180 ℃ after inserting in high-speed mixer and mixing fully.Then by rubber unvulcanizate after 180 ℃ of lower preheating 12min, insert in mould compacting 4min under 14.5Mpa and become sheet material.Then, go to while hot on flat-bed press, insert rapidly under the pressure of 14.5Mpa, cooling under not higher than 60 ℃, make the PVC plastics.
Embodiment 4
The nano-calcium carbonate that is 45nm by median size adds in the large flask that deionized water is housed, and flask is inserted in thermostat water bath, for flask installs homogenizer, stirring rod is inserted to the correct position below liquid level.Controlling bath temperature is 65 ℃.Start stirrer, the control rotating speed is 4000rpm.Add after stirring 9min and account for nano-calcium carbonate quality 1.1% Di(dioctylpyrophosphato) ethylene titanate, continue to stir 100min, make calcium carbonate and disperse liquid.By the median size of the nanoparticle in the Master2000 type laser particle size analyzer test calcium carbonate dispersion liquid of Britain Ma Erwen company, be 200nm.Then calcium carbonate is disperseed liquid successively filtered, dry, grind and cross 200 mesh sieves and obtain modified nano calcium carbonate.
Take the polyvinyl chloride resin quality as benchmark, and the modified nano calcium carbonate by 55%, 7% lead sulfate tribasic, 8% DOP and polyvinyl chloride resin are transferred in twin-roll plastic mixing mill mixing 13min under 190 ℃ after inserting in high-speed mixer and mixing fully.Then by rubber unvulcanizate after 180 ℃ of lower preheating 13min, insert in mould compacting 5min under 14.5Mpa and become sheet material.Then, go to while hot on flat-bed press, insert rapidly under the pressure of 14.5Mpa, cooling under not higher than 60 ℃, make the PVC plastics.
Embodiment 5
The nano-calcium carbonate that is 50nm by median size adds in the large flask that deionized water is housed, and flask is inserted in thermostat water bath, for flask installs homogenizer, stirring rod is inserted to the correct position below liquid level.Controlling bath temperature is 70 ℃.Start stirrer, the control rotating speed is 3500rpm.Add after stirring 10min and account for nano-calcium carbonate quality 1.4% Di(dioctylpyrophosphato) ethylene titanate, continue to stir 120min, make calcium carbonate and disperse liquid.By the median size of the nanoparticle in the Master2000 type laser particle size analyzer test calcium carbonate dispersion liquid of Britain Ma Erwen company, be 285nm.Then calcium carbonate is disperseed liquid successively filtered, dry, grind and cross 200 mesh sieves and obtain modified nano calcium carbonate.
Take the polyvinyl chloride resin quality as benchmark, and the modified nano calcium carbonate by 60%, 8% lead sulfate tribasic, 12% DOP and polyvinyl chloride resin are transferred in twin-roll plastic mixing mill mixing 15min under 185 ℃ after inserting in high-speed mixer and mixing fully.Then by rubber unvulcanizate after 185 ℃ of lower preheating 8min, insert in mould compacting 4min under 15Mpa and become sheet material.Then, go to while hot on flat-bed press, insert rapidly under the pressure of 15Mpa, cooling under not higher than 60 ℃, make the PVC plastics.
Embodiment 6
The nano-calcium carbonate that is 43nm by median size adds in the large flask that deionized water is housed, and flask is inserted in thermostat water bath, for flask installs homogenizer, stirring rod is inserted to the correct position below liquid level.Controlling bath temperature is 60 ℃.Start stirrer, the control rotating speed is 3500rpm.Add after stirring 8min and account for nano-calcium carbonate quality 1.0% Di(dioctylpyrophosphato) ethylene titanate, continue to stir 110min, make calcium carbonate and disperse liquid.By the median size of the nanoparticle in the Master2000 type laser particle size analyzer test calcium carbonate dispersion liquid of Britain Ma Erwen company, be 230nm.Then calcium carbonate is disperseed liquid successively filtered, dry, grind and cross 200 mesh sieves and obtain modified nano calcium carbonate.
Take the polyvinyl chloride resin quality as benchmark, and the modified nano calcium carbonate by 50%, 4% lead sulfate tribasic, 10% DOP and polyvinyl chloride resin are transferred in twin-roll plastic mixing mill mixing 10min under 185 ℃ after inserting in high-speed mixer and mixing fully.Then by rubber unvulcanizate after 180 ℃ of lower preheating 10min, insert in mould compacting 5min under 15Mpa and become sheet material.Then, go to while hot on flat-bed press, insert rapidly under the pressure of 15Mpa, cooling under not higher than 60 ℃, make the PVC plastics.
Comparative Examples
Adopt unmodified nano-calcium carbonate to prepare the PVC plastics, the preparation method is with embodiment 6.
To embodiment and Comparative Examples, to the consistency of nano-calcium carbonate and polyvinyl chloride resin, the contact angle by whiteruss viscosity and whiteruss characterizes.Wherein, the viscosity test process of nano-calcium carbonate is: whiteruss paste viscosity can be similar to and be equal to the viscosity of filler in PVC, the big or small direct reaction of viscosity goes out the consistency of nano-calcium carbonate and polyvinyl chloride resin, be viscosity more the bright nano-calcium carbonate of novel is better in the mobility of polyvinyl chloride resin, also just better with the consistency of polyvinyl chloride resin.This test adopts the digital viscometer of NDJ-5S of the prompt company of upper Helen to be tested viscosity.Adopt the German dataphysics OCA20 of company type contact angle measurement, embodiment and Comparative Examples are tested the contact angle of the whiteruss of nano-calcium carbonate.
The WDS-10 liquid crystal display electron tension testing machine that adopts the Jinan think of to reach test company carries out the test of tensile strength and elongation at break to the PVC plastics of embodiment and Comparative Examples.
Adopt the JBW-CY microcomputer-control full-automatic shock-testing machine of Jinan Memec testing installation company the PVC plastics of embodiment and Comparative Examples to be carried out to the test of resistance to impact shock.
Reference standard ASTM D2538-2002 does rheological test on the Plastograph-EC type torque rheometer of German Brabender company, and sample mass is 60.0g, and test temperature is 190 ℃, rotating speed 30rpm.
The above test result of embodiment and Comparative Examples is as follows:
As can be seen from the above table, embodiment is little than the unmodified nano-calcium carbonate of Comparative Examples through the whiteruss contact angle of the nano-calcium carbonate of Di(dioctylpyrophosphato) ethylene titanate modification, embodiment whiteruss viscosity is little than Comparative Examples, illustrates that thus nano-calcium carbonate through the Di(dioctylpyrophosphato) ethylene titanate modification has significantly improved the consistency with polyvinyl chloride resin.The elongation at break of embodiment, tensile strength and resistance to impact shock all want high than Comparative Examples.The fusion time of embodiment is shorter, and balancing torque and peak torque are less, and this illustrates that the former has rheological preferably.
Should be noted that and understand, in the situation that do not break away from the spirit and scope of accompanying claim the present invention for required protection, can make to the present invention of foregoing detailed description various modifications and improvement.Therefore, the scope of claimed technical scheme is not subject to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (8)
1. the method for a titanic acid ester modified nano calcium carbonate, is characterized in that, comprises the following steps:
(1) nano-calcium carbonate is added in deionized water, under the rotating speed of 2500～4000rpm, stir 5～10min;
(2) account for nano-calcium carbonate quality 0.4～1.4% Di(dioctylpyrophosphato) ethylene titanate to adding in the deionized water that is dispersed with nano-calcium carbonate through stirring, at the temperature of 50～70 ℃, stir 60～120min under the rotating speed of 2500～4000rpm, make calcium carbonate and disperse liquid;
(3) described calcium carbonate is disperseed in liquid to filter and drying, make modified nano calcium carbonate.
2. method according to claim 1, is characterized in that, described step (3) also comprises the modified nano calcium carbonate of drying is ground and sieves afterwards.
3. method according to claim 1, is characterized in that, in described step (1), the median size of nano-calcium carbonate is 30～50nm.
4. method according to claim 1, is characterized in that, in described step (3), the median size of modified nano calcium carbonate is 200～440nm.
5. a method that adopts modified nano calcium carbonate as claimed in claim 1 to prepare the PVC plastics, is characterized in that, comprises the following steps:
(1) take the polyvinyl chloride resin quality as benchmark, after the modified nano calcium carbonate by 30～60%, 3～8% lead sulfate tribasic, 2～12% DOP and polyvinyl chloride resin mix, carry out the mixing rubber unvulcanizate that obtains;
(2) rubber unvulcanizate is vulcanized, then cooling forming, make the PVC plastics.
6. method according to claim 5, is characterized in that, mixingly in described step (1) in twin-roll plastic mixing mill, carries out, and melting temperature is 170～190 ℃, and mixing time is 8～15min.
7. method according to claim 5, is characterized in that, in described step (2), sulfuration is specially: until after 175～185 ℃ of lower preheating 8～15min, insert in mould and suppress 2～5min one-tenth sheet material under 14～15Mpa.
8. method according to claim 5, is characterized in that, cooling forming is specially in described step (2): the cross-linked rubber obtained after sulfuration is gone on flat-bed press while hot, insert rapidly under the pressure of 14～15Mpa, and cooling under not higher than 60 ℃.
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Application publication date: 20140101 |