CN101451023B - Surface modified nano calcium carbonate and polychloroethylene plastisol thereof - Google Patents
Surface modified nano calcium carbonate and polychloroethylene plastisol thereof Download PDFInfo
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- CN101451023B CN101451023B CN200710124944XA CN200710124944A CN101451023B CN 101451023 B CN101451023 B CN 101451023B CN 200710124944X A CN200710124944X A CN 200710124944XA CN 200710124944 A CN200710124944 A CN 200710124944A CN 101451023 B CN101451023 B CN 101451023B
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- calcium carbonate
- nano calcium
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Abstract
The invention provides nano calcium carbonate with surface modification and polyvinyl chloride plastic sol thereof. Calcium oxide and carbon dioxide gas are used as raw material to synthesize the nano calcium carbonate; and after carbonizing reaction, the nano calcium carbonate is further subjected to surface modification treatment by taking carboxyl end group amilan polyamide resin as surface modifier, wherein the resin is prepared by condensation of fatty group polyprotic acid and fatty group polybasic amine, and the acid value is controlled between 50 and 500mgKOH/g. The invention also provides the polyvinyl chloride plastic sol added with the nano calcium carbonate, which comprises the following components by weight percentage: 10 to 25 percent of polyvinyl chloride resin, 0.2 to 5 percent of stabilizer, 20 to 45 percent of plasticizer, 0.2 to 8 percent of drying agent, 20 to 50 percent of common calcium carbonate filler, and 10 to 40 percent of nano calcium carbonate. Compared with the prior plastic sol, the polyvinyl chloride plastic sol, after solidification by a coating film, greatly improves impact resistance, and has good, anti-sag performance and adhesive force to electrophoresis of the polyvinyl chloride plastic sol.
Description
[technical field]
The present invention relates to the nano-calcium carbonate of a kind of nano-calcium carbonate and poly vinyl chloride plastisol, particularly a kind of surface-treated and adopts the poly vinyl chloride plastisol of this component.
[background technology]
Nano-calcium carbonate is meant the lime carbonate of particle diameter between the 1-100 nanometer, and the weighting material or the strengthening agent that can be used as coating, plastics, rubber, macromolecule resin etc. improve performance of products.Usually the Nano particles of calcium carbonate surface is hydrophilic oleophobic; And the nano-calcium carbonate of clad surface properties-correcting agent is not reunited easily; It is poor dispersion in organism; Bad with organic bonding properties, need carry out surface-treated strengthening itself and organic bonding properties, and prior art mainly is to adopt lipid acid or the resinous acid surface-modifying agent as nano-calcium carbonate.CN1400167A discloses a kind of nano-calcium carbonate that uses sodium soap as surface-modifying agent, and soap is at carbonic acid gas (CO
2) effect under change lipid acid into, therefore can regard that equally lipid acid is as surface-modifying agent as.The organic chain of lipid acid or resinous acid is short and be not with polar group, and with lipid acid or resinous acid as properties-correcting agent, the generation entanglement chance of the main body organic polymer in properties-correcting agent and coating or the rubber is few, molecular force is also little with it.Therefore adopt lipid acid or resinous acid as properties-correcting agent, in strong polar organic system, even adopt powerful dispersed with stirring, agglomeration still can take place in nano-calcium carbonate, and dispersion effect is unsatisfactory.
Nano-calcium carbonate for plastisol provides thixotropy, when constructing has good construction performance to guarantee plastisol as an important component in SE (PVC) the plastisol prescription.The fatty acid modified nano-calcium carbonate that adds in the prior art dispersed relatively poor in PVC, especially the bonding force with PVC is not strong, causes pvc plastisol not good to the sticking power of electrophoresis ground.And in order to solve the pvc plastisol problem not good to the sticking power of electrophoresis ground; Prior art is added resins such as polymeric amide, urethane again as tackifier in pvc plastisol; The method of adding is that tackifier directly are added in the plastisol prescription, and stirs and get final product.The direct dimer acid type polyamide tackifier that add in pvc plastisol are disclosed like CN 1982365A.Though such adding technology is simple, because of pvc plastisol viscosity is very big, cause the dispersiveness of tackifier in PVC peptization glue adhesive paste also bad, the tackifier adding proportion is also bigger, and the plastisol that obtains is not good to the sticking power of electrophoresis ground.
[summary of the invention]
The objective of the invention is in order to solve existing nano-calcium carbonate and the bad problem of polyvinyl chloride resin bonding properties; Provide a kind of and the strong surface modified nano calcium carbonate of polyvinyl chloride resin bonding force, also solved the problem of nano-calcium carbonate dispersion performance difference in organism simultaneously.
Another object of the present invention has provided the pvc plastisol that adds this surface modified nano calcium carbonate.
The invention provides a kind of surface modified nano calcium carbonate, this nano-calcium carbonate surface is coated with end carboxyl polyamides resin, and the acid number of said end carboxyl polyamides resin is 50-500mgKOH/g, preferred 100-400mgKOH/g.The inventor draws through a large amount of experiments; Acid number needs strict control; The too little end carboxyl polyamides resin that then makes of acid number is difficult for reacting to form covalent linkage with nano-calcium carbonate; It is synthetic that acid number too greatly then possibly make such carboxyl polyamides resin be difficult for, and causes synthetic cost to increase, and unhelpful to the nano-calcium carbonate adsorptive power in increasing.The median size of this nano-calcium carbonate is the 20-90 nanometer.
The preparation method of said nano-calcium carbonate, said method feed CO in quicklime (CaO) lime emulsion
2, after carburizing reagent is accomplished, in mixture, add end carboxyl polyamides resin, stir, to filter, drying obtains surface modified nano calcium carbonate.CaO content in the said lime emulsion is 3-10wt%, said CO
2Volumetric concentration be 20-40%, the acid number of said end carboxyl polyamides resin is the 0.5-10wt% of CaO at 50-500mgKOH/g, consumption.Said end carboxyl polyamides resin is formed by aliphatics polyprotonic acid and aliphatic polyamine condensation.
The present invention also provides a kind of pvc plastisol, comprises the polyvinyl chloride resin of 10-25wt%, the stablizer of 0.2-5wt%; The softening agent of 20-45wt%; The siccative of 0.2-8wt%, the ordinary calcium carbonate filler of 20-50wt% also comprises the nano-calcium carbonate of above-mentioned surface-treated; Addition is 10-40wt%, preferred 15-35wt%.Said nano-calcium carbonate surface is coating one deck end carboxyl polyamides resin, and the acid number of this end carboxyl polyamides resin is at 50-500mgKOH/g, preferred 100-400mgKOH/g.Said softening agent is selected from a kind of or youngster's kind in DOP (dinoctyl phthalate), DINP (Di Iso Decyl Phthalate), DBP (phthalic acid dibutyl ester), DEP (diethyl phthalate), BBP (butyl benzyl phthalate), the hot fat of Pyromellitic Acid four (different) (TOPM), tributyl acetylcitrate (ATBC), tributyl citrate, trioctyl phosphate, the diphenyl octyl phospbate.Said siccative is selected from the one or more combination in quicklime, calcium chloride, red oxide of iron, the silica gel.Said end carboxyl polyamides resin is formed by aliphatics polyprotonic acid and aliphatic polyamine condensation.The aliphatics polyprotonic acid can be that (it contains carbon number and is made as C for the unsaturated fatty acids of vegetables oil
2n, arbitrary integer of n=4-10) dimer (fatty acid) yl or three polyglycerol fatty acids.Aliphatic polyamine wherein is a quadrol, 1, one or more combination thing in 4-tetramethylenediamine, hexanediamine, NSC 446, the Triethylenetetramine (TETA).The a large amount of experiments of the inventor draw, and the amine groups number is many more, and unfavorable to the polymeric amide that generates high acid value more, too high like the amine value, then gathering diacid or trimer acid then needs ratio high more, is not easy the end carboxyl polyamides resin of synthetic high acid value more.
Added end carboxyl polyamides resin in the nano-calcium carbonate in the technical scheme of the present invention as surface-modifying agent.The strong polar group amino and the carboxyl of end carboxyl polyamides can provide good sticking power to the electrophoresis ground.And; End in the molecule contains the nonpolar long chain hydrocarbon groups that dimer (fatty acid) yl brings; The other end contains the polar carboxyl; This structural similitude is in exemplary surfactants, so it can form absorption with the high polar surfaces of calcium carbonate particles, can be embedded into well again in the plastisol in the polyvinyl chloride resin molecule.Because nano material has very high specific surface area, therefore, the polyamide resin among the present invention can form fully with nano-calcium carbonate and contact.Evenly be filled into the nano-calcium carbonate that coats end carboxyl polyamides resin in the pvc plastisol; And it is coated on the electrophoresis ground; Can increase plastisol Semi-polarity group amino greatly and lead with the youngster that contacts of carboxyl to ground, therefore, pvc plastisol thermoplastification postadhesion power significantly increases.Compared with prior art, can also reduce the consumption of organic resin, thereby reduce material cost.In the present invention; Mean length because of the nonpolar long chain hydrocarbon groups of dimer (fatty acid) yl in the end carboxyl polyamides resin; Length greater than alkyl in the lipid acid; Therefore, the nano-calcium carbonate that coats end carboxyl polyamides resin is better than the sour nano-calcium carbonate of prior art coated fat at the dispersing property of polyvinyl chloride resin, and this has very great help to the sticking power that improves pvc plastisol equally.And,, also can significantly improve the impact strength of plastisol plasticizing back rete because of the good dispersiveness of nano-calcium carbonate of the present invention.
[embodiment]
Embodiment 1
Get 100gCaO, add the 900ml deionized water, be heated to 65 ℃, fully stir the CO that feeds volume(tric)fraction 35% down
2, speed is 4L/min, stops ventilation after reaction 80min carbonization finishes; The end carboxyl polyamides resin (dimer and NSC 446 condensation by hard ester acid form) of 4g acid number at 120 ± 20mgKOH/g joined in the above-mentioned system; After continuing to stir 60min, at room temperature place 350min, filter; And, obtain the nano-calcium carbonate of the surface-treated of average primary particle diameter about 70 nanometers 60 ℃ of following dryings.
The surface modified nano calcium carbonate of present embodiment is joined in the automobile PVC plastisol prescription, at room temperature stir, obtain the pvc plastisol finished product.The composition of pvc plastisol and content are: polyvinyl chloride resin (model: E5/65C, Vinnolit company produces) accounts for 15wt%, filler (1000 order ordinary calcium carbonate; Wide Fujian material company produces) account for 30wt%, stablizer (model: REC852A, Guangdong Guang Yang high-tech industrial corporation produces) accounts for 2wt%; Softening agent (DOP, Nanjing, Nanjing petrochemical iy produced) accounts for 27.5wt%, siccative (CaO powder; Qingpu, Shanghai extraordinary quicklime factory produces) account for 0.5wt%, the nano-calcium carbonate of present embodiment accounts for 25wt%.
Embodiment 2
Except that 4g end carboxyl polyamides resin among the embodiment 1 is changed into the 8g, all the other are identical with embodiment 1.
Embodiment 3
Change the end carboxyl polyamides resin among the embodiment 1 into acid number and (can adjust the dimer of hard ester acid and the ratio of NSC 446 at the end carboxyl polyamides resin of 160 ± 20mgKOH/g; Obtain the end carboxyl polyamides resin of present embodiment acid number), all the other are identical with embodiment 1.
Embodiment 4
End carboxyl polyamides resin among the embodiment 1 is changed into by sad (C
8) the acid number that forms of dimer and 1,4 tetramethylenediamine condensation at 250 ± 20mgKOH/g end carboxyl polyamides resin, all the other are identical with embodiment 1.
Embodiment 5
End carboxyl polyamides resin among the embodiment 1 is changed into by myristic acid (C
14) the acid number that forms of dimer and 1,4 tetramethylenediamine condensation at 175 ± 20mgKOH/g end carboxyl polyamides resin, all the other are identical with embodiment 1.
Comparative Examples 1
Substitute coating the nano-calcium carbonate of holding the carboxyl polyamides resin to change into by the Triple Pressed Stearic Acid coating among the embodiment 1, all the other are identical with embodiment 1.
Comparative Examples 2
Filler in the Comparative Examples 1 is changed 27.5wt%, add polymeric amide tackifier 2.5wt% in addition, all the other are identical with Comparative Examples 1.
Performance test methods
(1) testing method of sticking power:
Sealer is painted the coating of 2 mm thick on the electrophoresis steel plate, 140-160 ℃ of baking half a hour, draw to the electrophoresis ground with cutter the cooling back, parallel stroke of twice, and spacing 5mm breaks off with the fingers and thumb with hand then, according to the grade of following standard determination sticking power size:
1 grade: no adhesivity, coating does not have sticking power or very soft and separate with ground to ground;
2 grades: beginning has adhesivity, and part adheres to fracture, and coating layer portion is retained on the ground or separates;
3 grades: what enough adhesivityes, coating were almost complete stays on the ground, only has a little to tear defective;
4 grades: good adhesivity, material self are torn (in gather fracture).
(2) sag prevention performance test methods:
Sealer is painted the coating of 5 mm thick on the electrophoresis steel plate, the vertical placement observed the perpendicular flow situation of coating, calculates (mm of unit) with the distance of overall flow after 20 minutes.
Good and bad according to following standard determination sag prevention performance: trickling 0mm is good, and trickling 0～3mm is qualified, trickles greater than 3mm for poor.
(3) measuring method of shock strength δ:
The car primary coat is painted the coating of 2 mm thick on the electrophoresis steel plate; 140-160 ℃ is toasted half a hour; The cooling back is with 50 centimetres of high shock tests of ram hammer of (>=10 newton) of certainweight; See whether come off, ftracture or puncture car primary coat coating, unit is NCM, general standard with >=500NCM is qualified.
Good and bad according to following standard determination shock strength performance:
δ >=900NCM is outstanding;
900NCM >=δ >=700NCM is good;
δ >=500NCM, it is qualified to be;
δ is less than 500NCM, and it is poor to be.
Test result
The The performance test results of above embodiment and comparative example is listed in the table 1 respectively.
Table 1
| Embodiment | The plastisol performance | ||
| Sticking power | The sag prevention performance | Impact strength δ/NCM | |
| Embodiment 1 | 4 grades | Do not trickle, good | δ >=900, outstanding |
| Embodiment 2 | 4 grades | Do not trickle, good | δ >=900, outstanding |
| Embodiment 3 | 4 grades | Do not trickle, good | 900 >=δ >=700, good |
| Embodiment 4 | 4 grades | Qualified | δ >=900, outstanding |
| Embodiment 5 | 4 grades | Do not trickle, good | 900 >=δ >=700, good |
| Comparative Examples 2 | 1 grade | Qualified | 700 >=δ >=500, qualified |
| Comparative Examples 3 | 3 grades | Qualified | 700 >=δ >=500, qualified |
Promptly adopt end carboxyl polyamides resin that nano-calcium carbonate is coated processing among the embodiment 1, the temperature that adopts during coating is 65 ℃, and the primary particle diameter of the nano-calcium carbonate that obtains is about 70 nanometers.This nano-calcium carbonate is joined in the automobile PVC plastisol prescription not extra interpolation tackifier.Can find out that from table 1 prepared plastisol is outstanding to the sticking power and the sag prevention performance of electrophoresis ground, and resistance to impact shock reaches more than the 900NCM, this is nano-calcium carbonate good embodiment of dispersing property in polyvinyl chloride resin of end carboxyl polyamides resin-coated.
Embodiment 2 from table 1 can find out that the addition of increase polyamide resin does not have big influence to the performance of nano-calcium carbonate.This embodiment explanation, end carboxyl polyamides amount of resin increases, and the effective covering amount on Namigai does not increase, and therefore the performance of PVC glue is not had influence.
Embodiment 3,4 and 5 from table 1 can find out that the increase of acid number helps obtaining well behaved nano-calcium carbonate, and the impact resistance of the pvc plastisol that makes is thus also promoted significantly.The dimeric structure of lipid acid influences the performance of nano-calcium carbonate too; The end carboxyl polyamides resin that the more lipid acid dimer condensation of carbon atom number forms is more suitable for coated nano calcium carbonate; The nano-powder that obtains is filled in the automobile PVC plastisol, the better performances of plastisol.
Comparative Examples 1 from table 1 can be found out; When adding nano-calcium carbonate that common Triple Pressed Stearic Acid coats in the pvc plastisol prescription; Do not add the polymeric amide tackifier; The sticking power of the pvc plastisol that obtains has only 1 grade, does not reach the industry requirement standard, and impact strength also only is being between 500～700NCM.Comparative Examples 2 is traditional P VC plastisol prescriptions; Though because added the polymeric amide tackifier, its sticking power can reach 3 grades, can reach the industry standard requirement; But its impact strength only is being between 500～700NCM, much smaller than the impact strength of the embodiment of the invention.
Therefore adopt the nano-calcium carbonate of end carboxyl polyamides resin-coated of the present invention well to solve existing nano-calcium carbonate and the bad problem of polyvinyl chloride resin bonding properties; Improved the resistance to impact shock of PVC; Also solved simultaneously the problem of nano-calcium carbonate dispersion performance difference in organism, and its sag prevention performance and also better to the sticking power of electrophoresis ground.
Claims (12)
1. a surface modified nano calcium carbonate is characterized in that, said nano-calcium carbonate surface is coated with end carboxyl polyamides resin, and the acid number of said end carboxyl polyamides resin is 50-500mgKOH/g; Said end carboxyl polyamides resin is formed by aliphatics polyprotonic acid and aliphatic polyamine condensation.
2. surface modified nano calcium carbonate according to claim 1 is characterized in that, said end carboxyl polyamides resinous acid value is 100-400mgKOH/g.
3. surface modified nano calcium carbonate according to claim 1 is characterized in that, the median size of surface modified nano calcium carbonate is the 20-90 nanometer.
4. surface modified nano calcium carbonate according to claim 1 is characterized in that, said aliphatic polyamine is a quadrol, 1, one or more combination in 4-tetramethylenediamine, hexanediamine, NSC 446, the Triethylenetetramine (TETA).
5. according to the preparation method of the said surface modified nano calcium carbonate of claim 1, said method is in quicklime lime emulsion, to feed carbonic acid gas, after carburizing reagent is accomplished; In mixture, add end carboxyl polyamides resin, stir, filter; Drying obtains surface modified nano calcium carbonate; Said end carboxyl polyamides resin is formed by aliphatics polyprotonic acid and aliphatic polyamine condensation.
6. according to the said method of claim 5; It is characterized in that; Calcium oxide content in the said lime emulsion is 3-10wt%, and the volumetric concentration of said carbonic acid gas is 20-40%, and the acid number of said end carboxyl polyamides resin is the 0.5-10wt% of said quicklime at 50-500mgKOH/g, consumption.
7. method according to claim 5 is characterized in that, said aliphatic polyamine is a quadrol, 1, one or more combination in 4-tetramethylenediamine, hexanediamine, NSC 446, the Triethylenetetramine (TETA).
8. poly vinyl chloride plastisol comprises the polyvinyl chloride resin of 10-25wt%, the stablizer of 0.2-5wt%; The softening agent of 20-45wt%; The siccative of 0.2-8wt%, the ordinary calcium carbonate filler of 20-50wt% is characterized in that; Also comprise surface modified nano calcium carbonate as claimed in claim 1, the addition of surface modified nano calcium carbonate is 10-40wt%.
9. poly vinyl chloride plastisol according to claim 8 is characterized in that, said nano-calcium carbonate surface is coated with end carboxyl polyamides resin, and the acid number of said end carboxyl polyamides resin is 50-500mgKOH/g.
10. poly vinyl chloride plastisol according to claim 8 is characterized in that, the addition of said surface modified nano calcium carbonate is 15-35wt%.
11. poly vinyl chloride plastisol according to claim 8; It is characterized in that said softening agent is selected from one or more in dinoctyl phthalate, Di Iso Decyl Phthalate, phthalic acid dibutyl ester, diethyl phthalate, butyl benzyl phthalate, the hot fat of Pyromellitic Acid four (different), tributyl acetylcitrate, tributyl citrate, trioctyl phosphate, the diphenyl octyl phospbate.
12. poly vinyl chloride plastisol according to claim 8 is characterized in that, said siccative is selected from the one or more combination in quicklime, calcium chloride, red oxide of iron, the silica gel.
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| CN200710124944XA CN101451023B (en) | 2007-12-04 | 2007-12-04 | Surface modified nano calcium carbonate and polychloroethylene plastisol thereof |
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| CN200710124944XA CN101451023B (en) | 2007-12-04 | 2007-12-04 | Surface modified nano calcium carbonate and polychloroethylene plastisol thereof |
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| CN101451023B true CN101451023B (en) | 2012-05-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105400238B (en) * | 2015-12-17 | 2018-02-16 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste |
| CN109537761A (en) * | 2016-06-14 | 2019-03-29 | 苏州杰姆斯特机械有限公司 | The ageing-resistant antistatic fireproof heat-preserving wall of one kind and its installation method |
| CN106013520B (en) * | 2016-06-14 | 2018-07-20 | 苏州杰姆斯特机械有限公司 | A kind of ageing-resistant antistatic tabula rasa room household of intelligence |
| ES2697908T3 (en) * | 2016-06-24 | 2019-01-29 | Omya Int Ag | Calcium carbonate surface treated as an extrusion adjuvant |
| CN108548913A (en) * | 2018-05-28 | 2018-09-18 | 廊坊立邦涂料有限公司 | A kind of detection device and detection method of the landing and adhesive force of electrophoretic coating glue |
| CN112724708B (en) * | 2021-01-11 | 2021-09-28 | 广西华纳新材料科技有限公司 | Surface treatment method of nano calcium carbonate for impact-resistant automobile chassis coating |
| CN116355466A (en) * | 2023-04-27 | 2023-06-30 | 广东时利和汽车实业集团有限公司 | PVC plastisol with high damping effect for automobile and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386169A (en) * | 1980-04-21 | 1983-05-31 | Rhone-Poulenc Industries | Polymer matrices reinforced with calcium carbonate particulates |
| CN1654551A (en) * | 2005-01-26 | 2005-08-17 | 上海大学 | Method for modifying nano calcium carbonate |
| CN1982365A (en) * | 2005-12-12 | 2007-06-20 | 上海理日化工新材料有限公司 | High-thixotropic poly(vinyl chloride) plastic sol |
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2007
- 2007-12-04 CN CN200710124944XA patent/CN101451023B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386169A (en) * | 1980-04-21 | 1983-05-31 | Rhone-Poulenc Industries | Polymer matrices reinforced with calcium carbonate particulates |
| CN1654551A (en) * | 2005-01-26 | 2005-08-17 | 上海大学 | Method for modifying nano calcium carbonate |
| CN1982365A (en) * | 2005-12-12 | 2007-06-20 | 上海理日化工新材料有限公司 | High-thixotropic poly(vinyl chloride) plastic sol |
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