CN116376112A - Nanometer calcium carbonate for promoting polypropylene nucleation and application thereof - Google Patents
Nanometer calcium carbonate for promoting polypropylene nucleation and application thereof Download PDFInfo
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- CN116376112A CN116376112A CN202310113090.4A CN202310113090A CN116376112A CN 116376112 A CN116376112 A CN 116376112A CN 202310113090 A CN202310113090 A CN 202310113090A CN 116376112 A CN116376112 A CN 116376112A
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- calcium carbonate
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- polypropylene
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 166
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 83
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 36
- -1 polypropylene Polymers 0.000 title claims abstract description 33
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 33
- 238000010899 nucleation Methods 0.000 title claims abstract description 15
- 230000006911 nucleation Effects 0.000 title claims abstract description 15
- 230000001737 promoting effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000004204 candelilla wax Substances 0.000 claims abstract description 24
- 229940073532 candelilla wax Drugs 0.000 claims abstract description 24
- 235000013868 candelilla wax Nutrition 0.000 claims abstract description 24
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 12
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000006011 modification reaction Methods 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 36
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007127 saponification reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002667 nucleating agent Substances 0.000 description 33
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 21
- 239000000920 calcium hydroxide Substances 0.000 description 21
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 21
- 239000007789 gas Substances 0.000 description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 13
- 235000011941 Tilia x europaea Nutrition 0.000 description 13
- 239000004571 lime Substances 0.000 description 13
- 238000003763 carbonization Methods 0.000 description 12
- 230000029087 digestion Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 230000032683 aging Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 3
- 239000011218 binary composite Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000008430 aromatic amides Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- BSWPEGCWMCHQJP-UHFFFAOYSA-L disodium [2,4-dibutyl-6-[(3,5-dibutyl-2-hydroxyphenyl)methyl]phenyl] phosphate Chemical group P(=O)([O-])([O-])OC1=C(C=C(C=C1CCCC)CCCC)CC1=C(C(=CC(=C1)CCCC)CCCC)O.[Na+].[Na+] BSWPEGCWMCHQJP-UHFFFAOYSA-L 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- CSJKPFQJIDMSGF-UHFFFAOYSA-K aluminum;tribenzoate Chemical compound [Al+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 CSJKPFQJIDMSGF-UHFFFAOYSA-K 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010942 self-nucleation Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical group [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses nano calcium carbonate for promoting polypropylene nucleation and application thereof. The preparation method of the nano calcium carbonate comprises the following steps: heating candelilla wax, adding an initiator and maleic anhydride, performing modification reaction under the condition of isolating oxygen to obtain a modifier 1, adding the modifier 1 into nano calcium carbonate suspension for activation reaction, adjusting pH to above 12.0 after the reaction is finished, adding 1-hydroxyethane-1, 1-diphosphonic acid for secondary modification reaction, performing filter pressing dehydration on the product, drying, crushing, grading and packaging to obtain the nano calcium carbonate for promoting polypropylene nucleation. The nano calcium carbonate product prepared by the invention has good compatibility with a polypropylene base material, high nucleation efficiency, simple process, low production cost, easy realization of industrial production and better economic and social benefits, and can effectively improve the beta crystalline phase proportion in the polypropylene material and the tensile strength and impact resistance of polypropylene.
Description
Technical Field
The invention relates to a preparation method of a polypropylene beta nucleating agent, in particular to nano calcium carbonate for promoting polypropylene nucleation and application thereof.
Background
Isotactic polypropylene (iPP) has become one of the most common commercial polymers at present due to its excellent mechanical properties and lower processing costs. iPP belongs to a typical semi-crystalline polymer, and the adjustment of crystallinity is critical to achieve the physical and mechanical properties of the final article. The technical means for improving the crystallinity of the iPP mainly comprises: (1) induced shear (orientation of the melt during processing); (2) applying a cooling temperature gradient; (3) Recrystallization of iPP melt molecular chains (self-nucleation of polymer chains), or addition of specific nucleating agents.
There are three known crystalline phases of iPP: alpha, beta and gamma. Of these, the alpha and beta phases are the most common crystallization modes of iPP. For iPP homopolymers, the alpha phase is thermodynamically stable and has a monoclinic crystal structure, which is relatively easy to produce. In contrast, beta phase is generally obtainable only by nucleation under specific process conditions, such as the addition of beta nucleating agents, many of which also contribute to the formation of alpha phase. The iPP crystallized by different crystalline phases has larger difference in mechanical properties, and the alpha phase has the functions of stiffening, improving the heat distortion temperature, creep resistance, improving the surface glossiness and the like, but the beta phase is obviously better than the alpha phase in the aspects of tensile breaking strength, breaking elongation, impact toughness and the like.
Beta nucleating agents are mainly divided into organic nucleating agents and inorganic nucleating agents. The common organic nucleating agent is mainly polycyclic aromatic hydrocarbon, organic carboxylic acid and salts thereof, and aromatic amide; the inorganic nucleating agent mainly comprises talcum powder, calcium carbonate, calcium silicate and the like. The main disadvantages of organic nucleating agents are high price, poor compatibility with polypropylene base materials and easy scaling in plastic processing equipment, while the main disadvantages of inorganic nucleating agents are poor nucleating efficiency and damage to original mechanical properties of base materials.
CN103087405B discloses a preparation method of binary composite polypropylene nucleating agent, nucleating agent prepared from the binary composite polypropylene nucleating agent and application of the nucleating agent. The nucleating agent is prepared by mixing and grinding inorganic nano particles and an organic nucleating agent, wherein the inorganic nano particles are attapulgite or silicon dioxide, and the organic nucleating agent is sodium 2,2' -methylene-bis (4, 6-di-n-butylphenol) phosphate. However, nano-scale silicon dioxide has strong agglomeration force, is not easy to disperse, is easy to form large agglomeration in a PP substrate, and has poor nucleation efficiency.
CN103788472a discloses a binary composite polypropylene nucleating agent, a preparation method and application. The nucleating agent consists of a benzoic acid nucleating agent and an organic nucleating agent, wherein the benzoic acid nucleating agent is sodium benzoate or aluminum benzoate; the organic nucleating agent is sodium 2,2' -methylene-bis (4, 6-di-n-butylphenol) phosphate. However, emulsion-like nucleating agents are difficult to form in practical applications in polypropylene plastics, and the presence of moisture can cause foaming and even degradation of the interior of the plastic.
CN103965545B discloses a polypropylene beta crystal form nucleating agent composition and a preparation method thereof. The polypropylene beta crystal form nucleating agent composition comprises an A nucleating agent and a B nucleating agent, wherein A is a carboxylate nucleating agent, and B is an aromatic amide beta nucleating agent. The invention only combines two different types of organic nucleating agents and cannot overcome the original defects.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides nano calcium carbonate for promoting polypropylene nucleation and application thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a nano calcium carbonate for promoting nucleation of polypropylene, the preparation method thereof comprising the steps of:
1) Heating candelilla wax to a molten state, adding an initiator and maleic anhydride, performing a modification reaction under the condition of isolating oxygen, and cooling for standby to obtain a modifier 1 after the reaction is completed;
2) Heating nano calcium carbonate suspension, adding a modifier 1 to perform an activation reaction, adjusting the pH to be more than 12.0 after the reaction is completed, and then adding 1-hydroxyethane-1, 1-diphosphonic acid to perform a secondary modification reaction to obtain modified nano calcium carbonate slurry;
3) And (3) carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry obtained in the step (2) to obtain the nano calcium carbonate for polypropylene nucleation.
In some examples, the initiator is selected from any one of benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butyl peroxybenzoate.
In some examples, the candelilla wax has a molecular weight of 700-900, a saponification number of 60-65, a lactone content of 2-5% in the chemical composition, and a resin acid content of 3-6%.
In some examples, the initiator is used in an amount of 0.1 to 0.3% by mass of the candelilla wax and the maleic anhydride is used in an amount of 2 to 4% by mass of the candelilla wax.
In some examples, the temperature of the modification reaction of step 1 is 90 to 95 ℃ and the reaction time is 4 to 5 hours.
In some examples, modifier 1 is used in an amount of 1.0 to 3.0% by mass of calcium carbonate and 1-hydroxyethane-1, 1-diphosphonic acid is used in an amount of 3.0 to 6.0% by mass of calcium carbonate.
In some examples, the activation reaction temperature of step 2 is 70-90 ℃ and the reaction time is 45-60 minutes.
In some examples, the time for the secondary modification reaction of step 2 is 2 to 3 hours.
In some examples, the specific surface area of the nano calcium carbonate suspension of the step 2 is 16-25 m 2 /g。
In some examples, the method of preparing the nano calcium carbonate suspension of step 2 is:
1) Slaking lime and tap water to react, removing impurities from slaked calcium hydroxide, and aging to obtain aged calcium hydroxide slurry;
2) Introducing CO into the aged calcium hydroxide slurry 2 And (3) performing carbonation reaction on the mixed gas until the pH value is less than or equal to 7.0, and obtaining the nano calcium carbonate suspension.
In some examples, the CO in step 2) 2 CO in mixed gas 2 The volume concentration is 28-35%.
In a second aspect, the invention provides an application of nano calcium carbonate in preparing a polypropylene nucleation promoter.
In a third aspect, the present invention provides a polypropylene material to which said nano calcium carbonate is added.
The beneficial effects of the invention are as follows:
1. the polypropylene beta nucleating agent nano calcium carbonate product prepared by the invention has good compatibility with a polypropylene base material, has high nucleating efficiency, and can effectively improve the proportion of beta crystalline phase in the polypropylene material.
2. The nano calcium carbonate product prepared by the invention can effectively improve the tensile strength and the shock resistance of polypropylene.
3. The invention has simple process, low production cost, easy realization of industrial production and better economic and social benefits.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different aspects of the invention.
Example 1
1) Preparation of nano calcium carbonate suspension: lime with calcium oxide content more than 90% is subjected to digestion reaction with tap water, the temperature of the digestion water is 40 ℃, and the mass ratio of the lime to the water is 1:4, a step of; removing impurities from the digested calcium hydroxide slurry through 80, 120 and 200 mesh vibrating screens respectively, and then aging for 24 hours; adjusting the concentration of the aged calcium hydroxide slurry to 8%, adjusting the temperature to 30 ℃, then conveying the aged calcium hydroxide slurry to a carbonization kettle, introducing kiln gas to carry out carbonation reaction, and controlling the kiln gas flow to 4000m 3 And/h until carbonization is completed (pH is less than or equal to 7.0), and the specific surface area is 16.4m 2 A/g nano calcium carbonate suspension;
2) Preparation of modifier 1: adding candelilla wax into a synthesis reaction kettle, heating to 90 ℃ to reach a molten state, adding 0.1% (calculated on candelilla wax dry basis) of tert-butyl peroxybenzoate as an initiator, then adding 3% (calculated on candelilla wax dry basis) of maleic anhydride, introducing nitrogen, reacting at 90 ℃ for 5 hours, and cooling to 70 ℃ for standby after the reaction is completed to obtain a modifier 1;
3) Preparation of nano calcium carbonate product: conveying carbonized nano calcium carbonate slurry to an activation kettle, heating to 70 ℃, adding a modifier 1 accounting for 1.0% of the dry basis mass of the nano calcium carbonate, and reacting for 45 minutes; after the activation is completed, adding ammonia water, adjusting the pH value of the reaction system to 12.2, adding 3.0 percent of 1-hydroxy ethane-1, 1-diphosphonic acid by the mass of the dry calcium carbonate, and continuing to react for 2 hours; and finally, carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry to obtain the special product.
Example 2
1) Preparation of nano calcium carbonate suspension: lime with calcium oxide content more than 90% is subjected to digestion reaction with tap water, the temperature of the digestion water is 60 ℃, and the mass ratio of the lime to the water is 1:6, preparing a base material; removing impurities from the digested calcium hydroxide slurry through 80, 120 and 200 mesh vibrating screens respectively, and then aging for 48 hours; the concentration of the aged calcium hydroxide slurry is regulated to 10 percent, the temperature is regulated to 25 ℃, then the aged calcium hydroxide slurry is conveyed to a carbonization kettle, kiln gas is introduced for carbonation reaction, and the kiln gas flow is controlled to be 4500m 3 And/h until carbonization is completed (pH is less than or equal to 7.0), and the specific surface area is 20.3m 2 A/g nano calcium carbonate suspension;
2) Preparation of modifier 1: adding candelilla wax into a synthesis reaction kettle, heating to 90 ℃ to reach a molten state, adding 0.3% (calculated on candelilla wax dry basis) of tert-butyl peroxybenzoate as an initiator, then adding 2% (calculated on candelilla wax dry basis) of maleic anhydride, introducing nitrogen, reacting for 4 hours at 90 ℃, and cooling to 70 ℃ for standby after the reaction is completed to obtain a modifier 1;
3) Preparation of nano calcium carbonate product: conveying carbonized nano calcium carbonate slurry to an activation kettle, heating to 80 ℃, adding modifier 1 accounting for 2.0% of the dry basis mass of the nano calcium carbonate, and reacting for 60 minutes; after the activation is completed, adding ammonia water, adjusting the pH value of the reaction system to 12.1, adding 4.5% of 1-hydroxyethane-1, 1-diphosphonic acid by the dry mass of calcium carbonate, and continuing to react for 3 hours; and finally, carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry to obtain the special product.
Example 3
1) Preparation of nano calcium carbonate suspension:lime with calcium oxide content more than 90% is subjected to digestion reaction with tap water, the temperature of the digestion water is 50 ℃, and the mass ratio of the lime to the water is 1:5, a step of; removing impurities from the digested calcium hydroxide slurry through 80, 120 and 200 mesh vibrating screens respectively, and then aging for 72 hours; the concentration of the aged calcium hydroxide slurry is regulated to 12 percent, the temperature is regulated to 20 ℃, then the aged calcium hydroxide slurry is conveyed to a carbonization kettle, kiln gas is introduced for carbonation reaction, and the kiln gas flow is controlled to 3500m 3 And/h until carbonization is completed (pH is less than or equal to 7.0), and the specific surface area is 24.7m 2 A/g nano calcium carbonate suspension;
2) Preparation of modifier 1: adding candelilla wax into a synthesis reaction kettle, heating to 90 ℃ to reach a molten state, adding 0.2% (calculated on candelilla wax dry basis) of tert-butyl peroxybenzoate as an initiator, then adding 4% (calculated on candelilla wax dry basis) of maleic anhydride, introducing nitrogen, reacting at 90 ℃ for 4.5 hours, and cooling to 70 ℃ for standby after the reaction is completed to obtain a modifier 1;
3) Preparation of nano calcium carbonate product: conveying carbonized nano calcium carbonate slurry to an activation kettle, heating to 90 ℃, adding modifier 1 accounting for 3.0% of the dry mass of the nano calcium carbonate, and reacting for 60 minutes; after the activation is completed, ammonia water is added, the pH value of the reaction system is adjusted to 12.3, and 1-hydroxyethane-1, 1-diphosphonic acid with the mass of 6.0 percent of the dry mass of calcium carbonate is added for continuous reaction for 2.5 hours; and finally, carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry to obtain the special product.
Example 4
1) Preparation of nano calcium carbonate suspension: lime with calcium oxide content more than 90% is subjected to digestion reaction with tap water, the temperature of the digestion water is 50 ℃, and the mass ratio of the lime to the water is 1:5, a step of; removing impurities from the digested calcium hydroxide slurry through 80, 120 and 200 mesh vibrating screens respectively, and then aging for 48 hours; the concentration of the aged calcium hydroxide slurry is regulated to 10 percent, the temperature is regulated to 23 ℃, then the aged calcium hydroxide slurry is conveyed to a carbonization kettle, kiln gas is introduced for carbonation reaction, and the kiln gas flow is controlled to 4000m 3 And/h until carbonization is completed (pH is less than or equal to 7.0), and the specific surface area is 23.5m 2 A/g nano calcium carbonate suspension;
2) Preparation of modifier 1: adding candelilla wax into a synthesis reaction kettle, heating to 90 ℃ to reach a molten state, adding 0.2% (calculated on candelilla wax dry basis) of tert-butyl peroxybenzoate as an initiator, then adding 3% (calculated on candelilla wax dry basis) of maleic anhydride, introducing nitrogen, reacting for 4 hours at 90 ℃, and cooling to 70 ℃ for standby after the reaction is completed to obtain a modifier 1;
3) Preparation of nano calcium carbonate product: conveying carbonized nano calcium carbonate slurry to an activation kettle, heating to 80 ℃, adding modifier 1 accounting for 2.5% of the dry basis mass of the nano calcium carbonate, and reacting for 60 minutes; after the activation is completed, ammonia water is added, the pH value of the reaction system is adjusted to 12.2, 5.0 percent of 1-hydroxy ethane-1, 1-diphosphonic acid with the dry mass of calcium carbonate is added, and the reaction is continued for 3 hours; and finally, carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry to obtain the special product.
Comparative example 1
The technical indexes of the commercial conventional nano calcium carbonate product are as follows: BET specific surface area 23.3m 2 Surface modification treatment was carried out with 4.0% sodium stearate.
Comparative example 2
Beta organic nucleating agents commonly used for commercially available polypropylene: DMDBS bis (3, 4-dimethylbenzylidene) sorbitol.
Comparative example 3
1) Preparation of nano calcium carbonate suspension: lime with calcium oxide content more than 90% is subjected to digestion reaction with tap water, the temperature of the digestion water is 50 ℃, and the mass ratio of the lime to the water is 1:5, a step of; removing impurities from the digested calcium hydroxide slurry through 80, 120 and 200 mesh vibrating screens respectively, and then aging for 48 hours; the concentration of the aged calcium hydroxide slurry is regulated to 10 percent, the temperature is regulated to 23 ℃, then the aged calcium hydroxide slurry is conveyed to a carbonization kettle, kiln gas is introduced for carbonation reaction, and the kiln gas flow is controlled to 4000m 3 And/h until carbonization is completed (pH is less than or equal to 7.0), and the specific surface area is 23.5m 2 A/g nano calcium carbonate suspension;
2) Preparation of modifier 1: adding candelilla wax into a synthesis reaction kettle, heating to 90 ℃ to reach a molten state, adding 0.2% (calculated on candelilla wax dry basis) of tert-butyl peroxybenzoate as an initiator, then adding 3% (calculated on candelilla wax dry basis) of maleic anhydride, introducing nitrogen, reacting for 4 hours at 90 ℃, and cooling to 70 ℃ for standby after the reaction is completed to obtain a modifier 1;
3) Preparation of nano calcium carbonate product: conveying carbonized nano calcium carbonate slurry to an activation kettle, heating to 80 ℃, adding modifier 1 accounting for 2.5% of the dry basis mass of the nano calcium carbonate, and reacting for 60 minutes; and finally, carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry to obtain the product of the comparative example.
Comparative example 4
1) Preparation of nano calcium carbonate suspension: lime with calcium oxide content more than 90% is subjected to digestion reaction with tap water, the temperature of the digestion water is 50 ℃, and the mass ratio of the lime to the water is 1:5, a step of; removing impurities from the digested calcium hydroxide slurry through 80, 120 and 200 mesh vibrating screens respectively, and then aging for 48 hours; the concentration of the aged calcium hydroxide slurry is regulated to 10 percent, the temperature is regulated to 23 ℃, then the aged calcium hydroxide slurry is conveyed to a carbonization kettle, kiln gas is introduced for carbonation reaction, and the kiln gas flow is controlled to 4000m 3 And/h until carbonization is completed (pH is less than or equal to 7.0), and the specific surface area is 23.5m 2 A/g nano calcium carbonate suspension;
2) Preparation of nano calcium carbonate product: conveying carbonized nano calcium carbonate slurry to an activation kettle, heating to 80 ℃, then adjusting the pH value of a reaction system to 12.2, adding 5.0% of 1-hydroxyethane-1, 1-diphosphonic acid by dry mass of calcium carbonate, and reacting for 3 hours; and finally, carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry to obtain the product of the comparative example.
Comparative analysis
The nucleator products of each of the examples and comparative examples of the present invention were extrusion pelletized by twin screws according to the following formulation:
| implementation project | Extrusion formulation |
| Examples 1 to 4, comparative examples 1, 3,4 | 100 parts of PP+2 parts of nano calcium carbonate |
| Comparative example 2 | 100 parts PP+0.25 parts DMDBS |
Crystallization performance test was analyzed by DSC differential scanning calorimetry (total crystallinity) and WAXD wide angle X-ray diffraction, see GB/T19466.3-2004; impact properties were tested according to GB/T1043.1-2008 standard; the tensile property is tested according to GB/T1040.2-2006 standard, the tensile rate is 20mm/min, and the beam displacement method is adopted; the bending performance is tested according to GB/T9341-2008 standard, and the summarized test results are shown in the following table:
as can be seen from the above table, examples 1 to 4 prepared by the method of the present invention can effectively improve the tensile strength and impact resistance of polypropylene, which is superior to comparative examples 1 to 2 prepared by commercial products; and as can be seen from comparative examples 3 and 4, the mechanical properties of the polypropylene material can be effectively improved by adopting the secondary modification to the conventional nano calcium carbonate.
The above description of the present invention is further illustrated in detail and should not be taken as limiting the practice of the present invention. It is within the scope of the present invention for those skilled in the art to make simple deductions or substitutions without departing from the concept of the present invention.
Claims (10)
1. The nano calcium carbonate for promoting polypropylene nucleation is characterized by comprising the following steps:
1) Heating candelilla wax to a molten state, adding an initiator and maleic anhydride, performing a modification reaction under the condition of isolating oxygen, and cooling for standby to obtain a modifier 1 after the reaction is completed;
2) Heating nano calcium carbonate suspension, adding a modifier 1 to perform an activation reaction, adjusting the pH to be more than 12.0 after the reaction is completed, and then adding 1-hydroxyethane-1, 1-diphosphonic acid to perform a secondary modification reaction to obtain modified nano calcium carbonate slurry;
3) And (3) carrying out filter pressing dehydration, drying, crushing, grading and packaging on the modified nano calcium carbonate slurry obtained in the step (2) to obtain the nano calcium carbonate for polypropylene nucleation.
2. The nano calcium carbonate according to claim 1, wherein the initiator is selected from any one of benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate and tert-butyl peroxybenzoate.
3. The nano calcium carbonate according to claim 1, wherein the candelilla wax has a molecular weight of 700-900, a saponification value of 60-65, a lactone content of 2-5% in chemical composition, and a resin acid content of 3-6%.
4. The nano calcium carbonate according to claim 1, wherein the initiator is used in an amount of 0.1 to 0.3% by mass of candelilla wax and the maleic anhydride is used in an amount of 2 to 4% by mass of candelilla wax.
5. The nano calcium carbonate according to claim 1, wherein the temperature of the modification reaction in the step 1 is 90-95 ℃ and the reaction time is 4-5 hours.
6. The nano calcium carbonate according to claim 1, wherein the modifier 1 is used in an amount of 1.0 to 3.0% by mass of calcium carbonate, and the 1-hydroxyethane-1, 1-diphosphonic acid is used in an amount of 3.0 to 6.0% by mass of calcium carbonate.
7. The nano calcium carbonate according to claim 1, wherein the activation reaction temperature of the step 2 is 70-90 ℃ and the reaction time is 45-60 minutes.
8. The nano calcium carbonate according to claim 1, wherein the time of the secondary modification reaction of the step 2 is 2 to 3 hours.
9. Use of the nano calcium carbonate according to claim 1 for preparing a polypropylene nucleation promoter.
10. A polypropylene material, wherein the nano calcium carbonate of claim 1 is added.
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| US20140364553A1 (en) * | 2011-12-31 | 2014-12-11 | Gch Technology Co., Ltd. | B-crystal form nucleating agent composition for polypropylene and use thereof |
| CN105924769A (en) * | 2016-04-29 | 2016-09-07 | 三门峡中达化工有限公司 | Method for modifying polypropylene material with complex of phosphate salt and nano-material |
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| US20140364553A1 (en) * | 2011-12-31 | 2014-12-11 | Gch Technology Co., Ltd. | B-crystal form nucleating agent composition for polypropylene and use thereof |
| CN103450556A (en) * | 2013-01-24 | 2013-12-18 | 长春天成高新纳米复合材料有限公司 | Preparation method of polypropylene phase-permeable nanoscale special homopolymerizing material |
| CN105924769A (en) * | 2016-04-29 | 2016-09-07 | 三门峡中达化工有限公司 | Method for modifying polypropylene material with complex of phosphate salt and nano-material |
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