CN1636878A - Prepn process of naometer calcium carbonate with non-polar surface - Google Patents
Prepn process of naometer calcium carbonate with non-polar surface Download PDFInfo
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- CN1636878A CN1636878A CN 200410052599 CN200410052599A CN1636878A CN 1636878 A CN1636878 A CN 1636878A CN 200410052599 CN200410052599 CN 200410052599 CN 200410052599 A CN200410052599 A CN 200410052599A CN 1636878 A CN1636878 A CN 1636878A
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- calcium carbonate
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Abstract
The preparation process of nano calcium carbonate with non-polar surface includes dispersing nano calcium carbonate particles in hot polypropylene solution homogeneously via high speed stirring; adding reactive monomer as modifier and initiating in-situ reaction of the reactive monomer with initiator under heat action to form macromolecular compatibilizing agent; and crystallizing polypropylene on the surface of nano calcium carbonate by means of the heterogeneous nucleation action of nano calcium carbonate on polypropylene under high speed stirring and slowly lowering temperature to obtain nano calcium carbonate particles with non-polar surface coated with reactive monomer grafted polypropylene. The composite nanometer calcium carbonate/polypropylene material with the nano calcium carbonate of the present invention added has high calcium carbonate dispersivity, raised interface adhesion, etc.
Description
Technical field
The invention belongs to the filling surface processing technology field, be specifically related to a kind of preparation method who uses the nano-calcium carbonate with apolar surfaces of reaction monomers graft polypropylene coating.
Background technology
Nano-calcium carbonate is as a kind of additive of polymkeric substance, has increment, fire-retardant, enhancing and toughening effect concurrently, but will play effective enhancing and toughening effect, must realize good dispersion and interface bonding.Because nano-calcium carbonate surface energy height, the tendency of reuniting is serious, big with the polypropylene polarity difference, consistency is poor, and the melt viscosity of polypropylene in the course of processing is big, make nano-calcium carbonate not reach effective dispersion and interface bonding, therefore in polypropylene, can not bring into play effective enhancing and toughening effect.Though dispersion agent commonly used can play dissemination, but the interface bonding is poor, traditional organic coupling agent is because organic chain is short, strengthen limited for the interface, the macromole compatilizer that development is played in the polymer blending capacity increasing technique has concurrently and disperses and coupled action, but, be difficult to enter and bring into play maximum utility between nanoparticle because viscosity is big.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with nano-calcium carbonate of apolar surfaces, after this nano-calcium carbonate adds polypropylene, can improve dispersiveness and interface adhesion simultaneously, to solve the nano-calcium carbonate surface energy height that prior art is handled, it is serious to reunite, the interface bonding is poor, is difficult to realize the problem of nano-dispersed in polymkeric substance.
Existing problems at the surface treatment method of existing nano-calcium carbonate, the present invention utilizes the polypropylene soltion viscosity of heat low, under high-speed stirring, Nano particles of calcium carbonate is uniformly dispersed by strong mechanical force, and the adding reactive monomer is as the method for properties-correcting agent, introduce multiple interfacial interaction at nano-calcium carbonate/polypropylene, utilize initiator initiation reaction monomer original position under heat effect to form the macromole compatilizer, the polarity part of macromole compatilizer is had an effect with nano-calcium carbonate, the nonpolar long-chain of macromole compatilizer and polyolefin substrate take place to tangle or cocrystallization, thereby various interfacial interactions in reinforced nano lime carbonate/polypropylene, and utilize nano-calcium carbonate to polyacrylic heterogeneous nucleation effect, slowly cooling in high-speed stirring, make polypropylene at the nano-calcium carbonate surface crystallization, obtain the Nano particles of calcium carbonate that uses the reaction monomers graft polypropylene to coat with apolar surfaces.Add in the nano-calcium carbonate/polypropylene composite material of this nano-calcium carbonate preparation, can improve the dispersiveness of nano-calcium carbonate, strengthen the interface bonding, strengthen tenacity-increased profax effectively.
The preparation method's of the nano-calcium carbonate with apolar surfaces of the present invention concrete steps and processing condition are as follows:
The a dosing: initiator and reactive monomer are dissolved in and obtain certain density initiator and reactive monomer mixing solutions in the benzene kind solvent;
B mixes: be heated to 180 ℃ of dissolvings in the benzene kind solvent that the polypropylene adding is identical with step a, obtain certain density polypropylene mixed solution, 120 ℃ of following high-speed stirring, add nano-calcium carbonate dry powder more in batches, obtain certain density polypropylene and nano-calcium carbonate mixed solution;
C reaction: continue 120 ℃ of following high-speed stirring, the initiator and the reaction monomers mixed solution that prepare among the step a are dropwise added in the mixed solution of step b, obtain the certain density mixed reaction solution that contains initiator, reactive monomer, polypropylene and nano-calcium carbonate, 120 ℃ of following constant temperature stirred reaction down more than 2 hours;
D cooling: slowly cool to room temperature under the high-speed stirring;
E filters, and drying is pulverized, and obtains the Nano particles of calcium carbonate with apolar surfaces that uses the reaction monomers graft polypropylene to coat.
The initiator of mentioning in the above step is a benzoyl peroxide, and reactive monomer can be vinylformic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, maleic anhydride.Benzene kind solvent can be a dimethylbenzene.In the reaction system, polyacrylic concentration is controlled at the 10-30 grams per liter, and the concentration of nano-calcium carbonate is controlled at the 25-50 grams per liter, and the concentration of benzoyl peroxide is controlled at the 0.25-0.6 grams per liter, and reactive monomer concentration is controlled at the 5-15 grams per liter.High-speed stirring mainly is to stir by the rotation that high speed agitator produces more than 300 rev/mins.
The Nano particles of calcium carbonate with apolar surfaces that the present invention prepares according to the method described above obviously reduces with respect to undressed nano-calcium carbonate surface energy polarity part, near the surface energy of phase emergencing copolymer; And with respect to pure polymkeric substance, Tc and melt temperature reduce; With respect to undressed calcium carbonate-filled polypropylene composite material, use Nano particles of calcium carbonate filled polypropylene to have good dispersiveness with apolar surfaces.
The present invention adds reactive monomer as in-situ modified dose in nano-calcium carbonate, polypropylene solution mixing process, can produce following effect:
1) nano-calcium carbonate is uniformly dispersed through high-speed stirring in polyacrylic dilute solution.
2) in the initiator effect, polypropylene backbone forms the reactive monomer graft polypropylene on the reactive monomer situ-formed graft, and perhaps the reactive monomer id reaction forms homopolymer.
3) physics and chemical action take place in polar group on reactive monomer graft polypropylene and the homopolymer thereof and nano-calcium carbonate surface, reunite thereby hinder nano-calcium carbonate.
4) slowly cooling under the high-speed stirring, polypropylene hinder nano-calcium carbonate and reunite in nano-calcium carbonate surface crystallization growth, form the little and Nano particles of calcium carbonate that has apolar surfaces uniformly of particle diameter.
5) because reactive monomer graft polypropylene and homopolymer thereof and nano-calcium carbonate have stronger effect, make polyacrylic crystalline growth be subjected to more obstruction with respect to pure polypropylene solution, crystallization and melt temperature reduce.
6) reactive monomer graft polypropylene and homopolymer thereof have physics chemical action and crystallization on nano-calcium carbonate, make the coating on nano-calcium carbonate surface very complete, and surface polarity obviously reduces, and approaches pure polypropylene.
Embodiment
Below the invention will be further described by specific embodiment.
The concentration proportioning and the correlated performance of embodiments of the invention are as shown in table 1.Wherein, Comparative Examples 1 is a nano-calcium carbonate, and Comparative Examples 2 is polypropylene, and embodiment 3,4 used reactive monomers are vinylformic acid, the used reactive monomer of embodiment 5-7 respectively is butyl acrylate, methyl methacrylate, maleic anhydride, and initiator is BPO.
The preparation method of each embodiment is as described in the summary of the invention part of front.
Weightless residual volume, crystallization and melt temperature under the surface tension of table 2 embodiment, 500 ℃
| Routine number | Nanometer CaCO3/ polypropylene/reaction monomers/initiator (concentration: grams per liter) | Surface tension/chromatic dispersion part/polarity part (mN/m) | 500 ℃ of following percent weight loss (wt %) | Tc (℃) | Melt temperature (℃) |
| Comparative Examples 1 | 100/0/0/0 | 52.3/16.1/36.2 | 0.7 | - | - |
| Comparative Examples 2 | 0/100/0/0 | 36/35.3/0.7 | 100 | 114.2 | 165.9 |
| Embodiment 3 | 40/10/10/0.1 | 36.8/36.1/0.7 | 30.0 | 109.9 | 165.3 |
| Embodiment 4 | 25/25/10/0.5 | 34.3/33.2/1.1 | 53.5 | 114.2 | 164.0 |
| Embodiment 5 | 40/10/10/0.1 | 37.1/36.4/0.7 | 25.3 | 114.6 | 164.6 |
| Embodiment 6 | 40/10/10/0.1 | 35.4/34.1/1.3 | 24.1 | 105.3 | 164.8 |
| Embodiment 7 | 40/10/10/0.1 | 36.2/35.7/0.5 | 24.5 | - | 164.4 |
1) surface tension is in surface tension instrument, adopts toluene, water, ethanol and dimethyl formamide to measure as solvent.
2) temperature rise rate of mensuration thermal weight loss per-cent is 10 ℃/min.
3) the lifting temperature speed of mensuration crystallization and melt temperature is 10 ℃/min.
Claims (10)
1. a method for preparing the nano-calcium carbonate with apolar surfaces is characterized in that this method comprises the following steps: in order
The a dosing: initiator and reactive monomer are dissolved in and obtain certain density initiator and reactive monomer mixing solutions in the benzene kind solvent;
B mixes: be heated to 180 ℃ of dissolvings in the benzene kind solvent that the polypropylene adding is identical with step a, obtain certain density polypropylene mixed solution, 120 ℃ of following high-speed stirring, add nano-calcium carbonate dry powder more in batches, obtain certain density polypropylene and nano-calcium carbonate mixed solution;
C reaction: continue 120 ℃ of following high-speed stirring, the initiator and the reaction monomers mixed solution that prepare among the step a are dropwise added in the mixed solution of step b, obtain the certain density mixed reaction solution that contains initiator, reactive monomer, polypropylene and nano-calcium carbonate, 120 ℃ of following constant temperature stirred reaction down more than 2 hours;
D cooling: slowly cool to room temperature under the high-speed stirring;
E filters, and drying is pulverized, and obtains the Nano particles of calcium carbonate with apolar surfaces that uses the reaction monomers graft polypropylene to coat.
2. according to the method for claim 1, it is characterized in that the described initiator of step a is a benzoyl peroxide.
3. according to the method for claim 1, it is characterized in that the described reactive monomer of step a is selected from vinylformic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, maleic anhydride.
4. according to the method for claim 1, it is characterized in that the described benzene kind solvent of step a is a dimethylbenzene.
5. according to the method for claim 1, it is characterized in that step a and the described benzene kind solvent of step b are 1: 4 by volume.
6. according to the method for claim 1, it is characterized in that initiator concentration is the 0.25-0.6 grams per liter in the described mixed reaction solution of step c.
7. according to the method for claim 1, the concentration that it is characterized in that reactive monomer in the described mixed reaction solution of step c is the 5-15 grams per liter.
8. according to the method for claim 1, it is characterized in that polyacrylic concentration is the 10-30 grams per liter in the described mixed reaction solution of step c.
9. according to the method for claim 1, the concentration that it is characterized in that nano-calcium carbonate in the described mixed reaction solution of step c is the 25-50 grams per liter.
10. according to the method for claim 1, it is characterized in that described high-speed stirring is to stir with the rotating paddle more than 300 rev/mins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410052599 CN1636878A (en) | 2004-12-09 | 2004-12-09 | Prepn process of naometer calcium carbonate with non-polar surface |
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| CN 200410052599 CN1636878A (en) | 2004-12-09 | 2004-12-09 | Prepn process of naometer calcium carbonate with non-polar surface |
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| CN1636878A true CN1636878A (en) | 2005-07-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623233A (en) * | 2016-02-26 | 2016-06-01 | 浙江森川家具有限公司 | Wear-resistant and scraping-resistant injection-molding-grade PC/ABS alloy material and preparing method thereof |
| CN112390985A (en) * | 2020-11-14 | 2021-02-23 | 际华三五一七橡胶制品有限公司 | Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur |
-
2004
- 2004-12-09 CN CN 200410052599 patent/CN1636878A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623233A (en) * | 2016-02-26 | 2016-06-01 | 浙江森川家具有限公司 | Wear-resistant and scraping-resistant injection-molding-grade PC/ABS alloy material and preparing method thereof |
| CN112390985A (en) * | 2020-11-14 | 2021-02-23 | 际华三五一七橡胶制品有限公司 | Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur |
| CN112390985B (en) * | 2020-11-14 | 2022-04-29 | 际华三五一七橡胶制品有限公司 | Preparation method of high-dispersion low-migration long-acting stable multilayer coated sulfur |
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