CN116675994A - High added value heavy calcium carbonate powder and production method thereof - Google Patents
High added value heavy calcium carbonate powder and production method thereof Download PDFInfo
- Publication number
- CN116675994A CN116675994A CN202310963113.0A CN202310963113A CN116675994A CN 116675994 A CN116675994 A CN 116675994A CN 202310963113 A CN202310963113 A CN 202310963113A CN 116675994 A CN116675994 A CN 116675994A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- heavy calcium
- activating
- activating machine
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 164
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 82
- 239000000843 powder Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 5
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 21
- 239000004033 plastic Substances 0.000 abstract description 21
- 230000004048 modification Effects 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000006870 function Effects 0.000 abstract description 4
- 125000005456 glyceride group Chemical group 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract 1
- 239000012190 activator Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 description 10
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 102000018779 Replication Protein C Human genes 0.000 description 6
- 108010027647 Replication Protein C Proteins 0.000 description 6
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 5
- -1 polybutylene terephthalate Polymers 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses high-added-value heavy calcium carbonate powder and a production method thereof, belonging to the technical field of calcium carbonate fine chemical industry. Wherein the heavy calcium carbonate powder comprises the following components: 98 to 99.4 percent of heavy calcium carbonate, 0.1 to 1.5 percent of modifier, 0.2 to 0.5 percent of dispersant and 0.05 to 0.1 percent of surfactant; the modifier is siloxane glyceride with ultra-long carbon chain. When the heavy calcium carbonate powder subjected to coupling treatment of the siloxane glyceride with the ultra-long carbon chain is added into a plastic matrix for modification, the winding action, the crosslinking reaction, the grafting reaction and the toughening action of the siloxane glyceride and the glyceride group in a blending system can occur. The functions are combined and overlapped, so that the mechanical property of the modified plastic blending system, particularly the improvement of the elongation at break and the impact strength, is obviously improved, and the dosage of the additive in the plastic modification process is obviously reduced.
Description
Technical Field
The invention relates to the technical field of calcium carbonate fine chemical industry, in particular to high-added-value heavy calcium carbonate powder and a production method thereof.
Background
The calcium carbonate has the advantages of rich natural resources, easy coloring, high whiteness, low hardness, excellent chemical stability, no toxicity and the like, and is widely applied to various industries or fields of papermaking, plastic or modified plastic, foam stabilizer, asphalt, film, rubber, paint, adhesive and the like. In practical industrial application, particularly in the application of modified plastic industry, in order to improve the binding force of calcium carbonate powder and matrix resin, the coupling treatment of the powder is adopted to become the consensus of the modified industry.
The powder subjected to coupling treatment by the coupling agent is applied to the plastic modification production process, and the contribution of the coupled powder to the mechanical property of the blending system is much smaller than that of the modifying agent.
In the process of calcium carbonate powder treatment, the mechanical property of the blending system is provided by modifying the calcium carbonate powder, so that the use amount of additives such as a modifier and the like in the plastic modification process is reduced, the production cost of modified plastic enterprises is reduced, the added value of the calcium carbonate is maximized, and the method is a key point and a difficult point of general attention in the field of calcium carbonate production.
Disclosure of Invention
The invention aims to solve the technical problem of providing high-added-value heavy calcium carbonate powder which is favorable for remarkably improving the mechanical property of a modified plastic blending system and remarkably reducing the additive amount in plastic modification and a production method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows: the high added value heavy calcium carbonate powder comprises the following components: 98 to 99.4 percent of heavy calcium carbonate, 0.1 to 1.5 percent of modifier, 0.2 to 0.5 percent of dispersant and 0.05 to 0.1 percent of surfactant;
wherein the modifier is siloxane glyceride with ultra-long carbon chain, and the structural formula is as follows:
；
wherein m, n and x are positive integers, and m+n+x is 13; r is R 1 Is that、/>、/>One of the following; r is R 2 Is- (CH) 2 ） 3 -、/>One of R 3 is-CH 3 、-OCH 3 、-OC 2 H 5 、-OC 3 H 7 One of the following; r is R 4 、R 5 respectively-OCH 3 、-OC 2 H 5 、-OC 3 H 7 One of them.
As an optimal technical scheme, the particle size of the heavy calcium carbonate is measured to be less than or equal to 1.100 mu m and less than or equal to D according to an European and American particle size tester 50 ≤4.300μm、5.500μm≤D 97 ≤14.000μm。
As a preferable technical scheme, the structure of the dispersing agent is Na-R, wherein R is polyacrylic acid group, dodecylbenzene sulfonic acid group or oleic acid group.
As a preferable technical scheme, the surfactant is one of dodecyl dimethyl benzyl ammonium chloride, triethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride.
The production method of the high-added-value heavy calcium carbonate powder adopts a gravity-free mixer to be combined with a three-roller activator for production, wherein three-roller activators are respectively a primary activator, a secondary activator and a tertiary activator which are sequentially arranged; the three-roller activating machine comprises an activating machine cavity, wherein a main shaft is rotatably arranged in the activating machine cavity, a plurality of auxiliary shafts which are radially extended are arranged on the main shaft, and a plurality of paddles are respectively arranged on each auxiliary shaft; the main shaft extends out of the cavity of the activating machine and is connected with an activating driving motor; the method comprises the following production steps:
step one: heating the gravity-free mixer to 80 ℃;
step two: diluting the surfactant with distilled water with the mass fraction of 10 times;
step three: placing the heavy calcium carbonate into the gravity-free mixer, and heating to 80 ℃ under the stirring state;
step four: uniformly adding the dispersing agent according to a proportion, wherein the adding control time of the dispersing agent is 30-60 s;
step five: uniformly adding the surfactant diluted according to the second step by adopting a metering pump, wherein the adding time is controlled to be 120-150 s;
step six: continuously mixing for 3-5 minutes, and then adding the modifier by adopting a metering pump, wherein the adding time is controlled to be 60-120 seconds;
step seven: mixing for 5-7 minutes and discharging;
step eight: feeding the discharged mixed material into the primary activating machine by adopting an auger; the mixed material enters the secondary activating machine under the action of high-speed rotation and inertia force of the blades in the primary activating machine, and then enters the tertiary activating machine under the action of high-speed rotation and inertia force of the blades in the secondary activating machine; in the three-stage three-roller activating machine, the mixed material is continuously subjected to shearing, friction and collision, and the temperature is rapidly increased, so that the hydroxyl on the surface of the calcium carbonate is activated, and the hydroxyl on the main chain of the modifier is subjected to condensation reaction to form an '-O' -bond, so that the firm combination of the modifier and the calcium carbonate is realized;
step nine: the powder after being activated by the three-roller activating machine is blown to the classifier by a fan, and after being screened and classified by the classifier, the qualified powder enters a bag filter for collection treatment, and large particles formed by agglomeration or adhesion of a modifier return to the primary activating machine and enter the activating treatment again;
step ten: and transferring the qualified powder collected by the bag filter to a finished product bin, discharging from the finished product bin, and packaging the finished product.
By adopting the technical scheme, when the heavy calcium carbonate powder subjected to coupling treatment of the siloxane glyceride with the ultra-long carbon chain is added into a plastic matrix for modification, the following interactions can occur: (1) The ultra-long carbon chain can be wound with the plastic matrix due to the sufficient carbon chain length; (2) Double bond opening or R on main chain 1 When the propenyl is adopted, double bonds on the propenyl are opened to generate a crosslinking reaction, so that a rubber phase is formed and dispersed in a blending system; (3) When the matrix material is a material having poor high temperature stability (such as a copolymer of butanediol adipate and polybutylene terephthalate (PBAT), polylactic acid (PLA), polyamide (PA), etc.), the double bond in the main chain is opened or R 1 When the propenyl is adopted, double bonds on the propenyl are opened to generate grafting reaction with the matrix materials; (4) The siloxane groups and glyceride groups in the siloxane glyceride with ultra-long carbon chains play a role in toughening in the blending system. The functions are combined and overlapped, so that the heavy calcium carbonate powder treated by the ultra-long carbon chain siloxane glyceride modifier can obviously improve the mechanical properties of a modified plastic blending system, particularly the improvement of elongation at break and impact strength, and simultaneously the additive dosage in the plastic modification process is obviously reduced, and the application added value of the heavy calcium carbonate powder is higher.
Drawings
The following drawings are only for purposes of illustration and explanation of the present invention and are not intended to limit the scope of the invention. Wherein:
FIG. 1 is a schematic diagram of the structural principle of a three-roll activator according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a specific construction of one of the three-roll activators of fig. 1.
In the figure: 1-a three-roller activator; 11-a primary activator; a 12-secondary activator; 13-a three-stage activating machine; 14-an activator chamber; 15-a main shaft; 16-lay shaft; 17-paddle; 2-a fan; 3-classifier.
Detailed Description
The invention is further illustrated in the following, in conjunction with the accompanying drawings and examples. In the following detailed description, exemplary embodiments of the invention are described by way of illustration only. It is needless to say that the person skilled in the art realizes that the described embodiments may be modified in various different ways without departing from the spirit and scope of the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive in scope.
The high added value heavy calcium carbonate powder comprises the following components: 98 to 99.4 percent of heavy calcium carbonate, 0.1 to 1.5 percent of modifier, 0.2 to 0.5 percent of dispersant and 0.05 to 0.1 percent of surfactant.
Wherein the particle size of the heavy calcium carbonate is 1.100 mu m less than or equal to D according to the measurement of European and American particle size tester 50 ≤4.300μm、5.500μm≤D 97 ≤14.000μm。
The modifier is siloxane glyceride with ultra-long carbon chains, and the structural formula is as follows:
；
wherein m, n and x are positive integers, and m+n+x is 13; r is R 1 Is that、/>、One of the following; r is R 2 Is- (CH) 2 ） 3 -、/>One of R 3 is-CH 3 、-OCH 3 、-OC 2 H 5 、-OC 3 H 7 One of the following; r is R 4 、R 5 respectively-OCH 3 、-OC 2 H 5 、-OC 3 H 7 One of them.
The preparation of the siloxane glyceride with the ultra-long carbon chain is a known technology and can be prepared according to the preparation method disclosed in the patent with the publication number of CN103467510B, namely the preparation method of the oil source silane coupling agent with the toughening function.
The mechanism of action of the siloxane-based glyceride with an ultra-long carbon chain is as follows: CO on the surface of heavy calcium carbonate under long-term geological environment condition 3 2- The ions can be replaced by the chemical adsorption of moisture in the atmosphere in a considerable proportion, and as a result of the hydrolysis, a large amount of hydroxyl structures exist on the surface of the particles, and after the siloxane glyceride with an ultra-long carbon chain is mixed with the calcium carbonate at a high temperature, the hydroxyl groups on the main chain of the siloxane glyceride with the ultra-long carbon chain are combined with the hydroxyl groups on the surface of the calcium carbonate to generate an '-O' -bond, so that the siloxane glyceride with the ultra-long carbon chain is combined with the calcium carbonate to realize coupling.
The structure of the dispersing agent is Na-R, wherein R is polyacrylic acid group, dodecyl benzene sulfonic acid group or oleic acid group, namely the dispersing agent is one of sodium polyacrylate, sodium dodecyl benzene sulfonate and sodium oleate. The structure is slightly alkaline, but after the dispersing agent is applied to the heavy calcium carbonate, negative charges in molecules can lead particles to generate static electricity so as to generate a repulsive phenomenon, thereby playing a role of dispersing the particles.
The surfactant is one of dodecyl dimethyl benzyl ammonium chloride, triethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride. The dual structure of the surfactant reduces the chemical energy of the surface of heavy calcium carbonate, and further assists the dispersant in preventing calcium carbonate from agglomerating.
When the heavy calcium carbonate powder subjected to coupling treatment of the siloxane glyceride with an ultra-long carbon chain is added into a plastic matrix for modification, the following interactions occur: (1) The ultra-long carbon chain can be wound with the plastic matrix due to the sufficient carbon chain lengthThe method comprises the steps of carrying out a first treatment on the surface of the (2) Double bond opening or R on main chain 1 When the propenyl is adopted, double bonds on the propenyl are opened to generate a crosslinking reaction, so that a rubber phase is formed and dispersed in a blending system; (3) When the matrix material is a material having poor high temperature stability (such as a copolymer of butanediol adipate and polybutylene terephthalate (PBAT), polylactic acid (PLA), polyamide (PA), etc.), the double bond in the main chain is opened or R 1 When the propenyl is adopted, double bonds on the propenyl are opened to generate grafting reaction with the matrix materials; (4) The siloxane groups and glyceride groups in the siloxane glyceride with ultra-long carbon chains play a role in toughening in the blending system. The functions are combined and overlapped, so that the heavy calcium carbonate powder modified by the siloxane glyceride with an ultra-long carbon chain can obviously improve the mechanical properties of a modified plastic blending system, particularly the improvement of the elongation at break and the impact strength, and meanwhile, the additive dosage in the plastic modification process is obviously reduced, and the application added value of the heavy calcium carbonate powder is higher.
The production method of the high-added-value heavy calcium carbonate powder adopts a gravity-free mixer to be combined with a three-roller activator 1 for production, wherein the three-roller activator 1 is provided with three, as shown in figure 1, the three-roller activators 1 are respectively a primary activator 11, a secondary activator 12 and a tertiary activator 13 which are sequentially arranged; as shown in fig. 2, the three-roller activator 1 comprises an activator cavity 14, a main shaft 15 is rotatably installed in the activator cavity 14, a plurality of auxiliary shafts 16 extending radially are installed on the main shaft 15, and a plurality of paddles 17 are respectively arranged on each auxiliary shaft 16; the main shaft 15 extends out of the activating machine cavity 14 and is connected with an activating drive motor; the method comprises the following production steps:
step one: heating the gravity-free mixer to 80 ℃;
step two: diluting the surfactant with distilled water with the mass fraction of 10 times;
step three: placing the heavy calcium carbonate into the gravity-free mixer, and heating to 80 ℃ under the stirring state;
step four: uniformly adding the dispersing agent according to a proportion, wherein the adding control time of the dispersing agent is 30-60 s;
step five: uniformly adding the surfactant diluted according to the second step by adopting a metering pump, wherein the adding time is controlled to be 120-150 s;
step six: continuously mixing for 3-5 minutes, and then adding the modifier by adopting a metering pump, wherein the adding time is controlled to be 60-120 seconds;
step seven: mixing for 5-7 minutes and discharging;
step eight: feeding the discharged mixed material into the primary activator 11 by adopting a screw; preferably, each stage of the three-roller activator 1 is a high-speed rotary activator; the mixed material enters the secondary activating machine 12 under the action of high-speed rotation and inertia force of the blades 17 in the primary activating machine 11, and then enters the tertiary activating machine 13 under the action of high-speed rotation and inertia force of the blades 17 in the secondary activating machine 12; in the three-stage three-roller activator 1, the mixed material is continuously sheared, rubbed and collided by the powder and the paddle 17, the powder and the powder, and the powder and the cavity wall of the activator cavity 14, the temperature is rapidly increased, so that the hydroxyl on the surface of the calcium carbonate is activated, and the hydroxyl on the main chain of the modifier is subjected to condensation reaction to form an '-O' -bond, so that the firm combination of the modifier and the calcium carbonate is realized;
step nine: the powder after being activated by the three-roller activator 1 is blown to the classifier 3 by the fan 2, and after being screened and classified by the classifier 3, the qualified powder enters a bag filter for collection treatment, and large particles formed by agglomeration or adhesion of a modifier return to the first-stage activator 11 and enter the activation treatment again;
step ten: and transferring the qualified powder collected by the bag filter to a finished product bin, discharging from the finished product bin, and packaging the finished product.
By adopting different modifier structures and raw material proportions, the heavy calcium carbonate powder with different high added values can be produced, and the heavy calcium carbonate powder is particularly described in the following examples.
Example 1:
the mass fraction is 98.95 percent, and the grain diameter D is adopted 50 1.555 μm, D 97 5.564 μm heavy calcium carbonate with 0.5% sodium oleate as dispersing agentThe agent takes 0.05 percent of dodecyl dimethyl benzyl ammonium chloride as a surfactant, and adopts the components with the mass fraction of 0.5 percent, the m+n+x of 13 and R 1 Is that、R 2 Is- (CH) 2 ） 3 -、R 3 is-CH 3 、R 4 And R is 5 Are all-OCH 3 And (3) producing the high-added-value heavy calcium carbonate powder by using the siloxane glyceride with the ultra-long carbon chain.
The produced high added value heavy calcium carbonate powder and high density polyethylene are respectively mixed according to the mass fractions of 30% and 70%, and after being subjected to sheet milling by an open mill, the high added value heavy calcium carbonate powder and the high density polyethylene are subjected to sheet milling by a flat vulcanizing machine to test the tensile strength and the elongation at break.
Example 2:
the mass fraction is 98.7 percent, and the grain diameter is D 50 1.555 μm, D 97 5.564 μm heavy calcium carbonate, sodium oleate 0.2% as dispersant, cetyltrimethylammonium chloride 0.1% as surfactant, 1% m+n+x 13, R 1 Is that、R 2 Is->、R 3 、R 4 And R is 5 Are all-OC 3 H 7 And (3) producing the high-added-value heavy calcium carbonate powder by using the siloxane glyceride with the ultra-long carbon chain.
The produced high added value heavy calcium carbonate powder and high density polyethylene are respectively mixed according to the mass fractions of 30% and 70%, and after being subjected to sheet milling by an open mill, the high added value heavy calcium carbonate powder and the high density polyethylene are subjected to sheet milling by a flat vulcanizing machine to test the tensile strength and the elongation at break.
Comparative example 1:
activating the particle size D by adopting a silane coupling agent KH550 with the mass fraction of 1 percent 50 1.555 μm, D 97 The weight of the heavy calcium carbonate is 5.564 mu m, the obtained heavy calcium carbonate and the high-density polyethylene are respectively mixed according to the mass fractions of 30 percent and 70 percent, and an open mill is adoptedAfter the sheet was formed, the tensile strength and elongation at break were measured by tabletting with a press, and the data were compared with examples 1 and 2.
Example 3:
the mass fraction is 99.4 percent, and the grain diameter D is adopted 50 4.252 μm, D 97 13.116 μm heavy calcium carbonate, sodium oleate with mass fraction of 0.2% as dispersant, benzyl trimethyl ammonium chloride with mass fraction of 0.1% as surfactant, and m+n+x of 0.3% as 13, R 1 Is that、R 2 Is- (CH) 2 ） 3 -、R 3 、R 4 And R is 5 Are all-OC 2 H 5 And (3) producing the high-added-value heavy calcium carbonate powder by using the siloxane glyceride with the ultra-long carbon chain.
The produced high added value heavy calcium carbonate powder and the co-polypropylene are mixed according to the mass fractions of 30% and 70%, and after being granulated by a granulator, the cantilever impact strength of the high added value heavy calcium carbonate powder and the co-polypropylene is tested by an injection molding machine through injection molding impact splines.
Comparative example 2:
by particle diameter D 50 4.252 μm, D 97 The weight calcium carbonate of 13.116 μm and the polypropylene copolymer were mixed according to the mass fractions of 30% and 70%, and after pelleting by a pelleting machine, the cantilever impact strength was tested by injection molding impact bars by an injection molding machine, and the data were compared with example 3.
Example 4:
the mass fraction is 99.15 percent, and the grain diameter D is adopted 50 Heavy calcium carbonate with 2.232 mu m and D97 8.815 mu m, sodium oleate with mass fraction of 0.2% as dispersing agent, dodecyl dimethyl benzyl ammonium chloride with mass fraction of 0.05% as surfactant, m+n+x of 13 and R 1 Is that、R 2 Is- (CH) 2 ） 3 -、R 3 、R 4 And R is 5 Are all-OC 2 H 5 Is used for producing high added value heavy carbon by using siloxane glyceride with ultra-long carbon chainCalcium acid powder.
The produced high-added-value heavy calcium carbonate powder is mixed with 35% and 65% of copolymer (PBAT) of butanediol adipate and polybutylene terephthalate according to mass fractions, and after granulating by a granulator, the tensile strength and the elongation at break of the high-added-value heavy calcium carbonate powder are tested by an injection molding machine through injection molding tensile bars.
Example 5:
the mass fraction is 98.08 percent, and the grain diameter D is adopted 50 Is 2.232 mu m, D 97 8.815 μm heavy calcium carbonate, sodium oleate 0.35% as dispersant, benzyl trimethyl ammonium chloride 0.07% as surfactant, 1.5% by weight, m+n+x 13, R 1 Is that，R 2 Is- (CH) 2 ） 3 -、R 3 、R 4 And R is 5 Are all-OC 2 H 5 And (3) producing the high-added-value heavy calcium carbonate powder by using the siloxane glyceride with the ultra-long carbon chain.
The produced high-added-value heavy calcium carbonate powder is mixed with 35% and 65% of copolymer (PBAT) of butanediol adipate and polybutylene terephthalate according to mass fractions, and after granulating by a granulator, the tensile strength and the elongation at break of the high-added-value heavy calcium carbonate powder are tested by an injection molding machine through injection molding tensile bars.
Comparative example 3:
coupling particle diameter D by using titanate coupling agent with mass fraction of 2% 50 Is 2.232 mu m, D 97 The resultant copolymer (PBAT) of heavy calcium carbonate with a mass fraction of 35% and 65% of butylene adipate and butylene terephthalate was compounded as 8.815 μm heavy calcium carbonate, and after pelleting by a pelleting machine, tensile strength and elongation at break were measured by injection molding of tensile bars by an injection molding machine, and the data were compared with those of examples 4 and 5.
The mechanical properties of each example are shown in Table 1 in comparison with those of the comparative examples.
Table 1 comparison of mechanical properties of examples and comparative examples
The comparative examples and the comparative examples both use the same heavy calcium carbonate and the same plastic base. The following conclusions can be drawn from the comparison of the above examples with the comparative examples: the high-added-value heavy calcium carbonate powder modified high-density polyethylene, the copolymer polypropylene or the copolymer (PBAT) of the butanediol adipate and the butanediol terephthalate produced by the embodiment shows more outstanding mechanical properties than the comparative example, has more remarkable additional effects besides the coupling effect, and is particularly outstanding in the aspects of elongation at break and impact strength. The outstanding added value ensures that the use of the modified heavy calcium carbonate powder is beneficial to obviously reducing the dosage of the additive in the comparative formula system and is extremely beneficial to reducing the formula cost in the production of modified plastics.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (5)
1. The high-added-value heavy calcium carbonate powder is characterized by comprising the following components: 98 to 99.4 percent of heavy calcium carbonate, 0.1 to 1.5 percent of modifier, 0.2 to 0.5 percent of dispersant and 0.05 to 0.1 percent of surfactant;
wherein the modifier is siloxane glyceride with ultra-long carbon chain, and the structural formula is as follows:
；
wherein m, n and x are positive integers, and m+n+x is 13; r is R 1 Is that、/>、/>One of the following; r is R 2 Is- (CH) 2 ） 3 -、/>One of R 3 is-CH 3 、-OCH 3 、-OC 2 H 5 、-OC 3 H 7 One of the following; r is R 4 、R 5 respectively-OCH 3 、-OC 2 H 5 、-OC 3 H 7 One of them.
2. The high value-added heavy calcium carbonate powder according to claim 1, characterized in that: the particle size of the heavy calcium carbonate is measured to be less than or equal to 1.100 mu m and less than or equal to D according to an European and American particle size tester 50 ≤4.300μm、5.500μm≤D 97 ≤14.000μm。
3. The high value-added heavy calcium carbonate powder according to claim 1, characterized in that: the structure of the dispersing agent is Na-R, wherein R is polyacrylic acid group, dodecylbenzene sulfonic acid group or oleic acid group.
4. The high value-added heavy calcium carbonate powder according to claim 1, characterized in that: the surfactant is one of dodecyl dimethyl benzyl ammonium chloride, triethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride.
5. The production method of the high added value heavy calcium carbonate powder according to any one of claims 1 to 4, wherein a gravity-free mixer is used for production in combination with three-roller activating machines, three of the three-roller activating machines are respectively a primary activating machine, a secondary activating machine and a tertiary activating machine which are sequentially arranged; the three-roller activating machine comprises an activating machine cavity, wherein a main shaft is rotatably arranged in the activating machine cavity, a plurality of auxiliary shafts which are radially extended are arranged on the main shaft, and a plurality of paddles are respectively arranged on each auxiliary shaft; the main shaft extends out of the cavity of the activating machine and is connected with an activating driving motor; the method comprises the following production steps:
step one: heating the gravity-free mixer to 80 ℃;
step two: diluting the surfactant with distilled water with the mass fraction of 10 times;
step three: placing the heavy calcium carbonate into the gravity-free mixer, and heating to 80 ℃ under the stirring state;
step four: uniformly adding the dispersing agent according to a proportion, wherein the adding control time of the dispersing agent is 30-60 s;
step five: uniformly adding the surfactant diluted according to the second step by adopting a metering pump, wherein the adding time is controlled to be 120-150 s;
step six: continuously mixing for 3-5 minutes, and then adding the modifier by adopting a metering pump, wherein the adding time is controlled to be 60-120 seconds;
step seven: mixing for 5-7 minutes and discharging;
step eight: feeding the discharged mixed material into the primary activating machine by adopting an auger; the mixed material enters the secondary activating machine under the action of high-speed rotation and inertia force of the blades in the primary activating machine, and then enters the tertiary activating machine under the action of high-speed rotation and inertia force of the blades in the secondary activating machine; in the three-stage three-roller activating machine, the mixed material is continuously subjected to shearing, friction and collision, and the temperature is rapidly increased, so that the hydroxyl on the surface of the calcium carbonate is activated, and the hydroxyl on the main chain of the modifier is subjected to condensation reaction to form an '-O' -bond, so that the firm combination of the modifier and the calcium carbonate is realized;
step nine: the powder after being activated by the three-roller activating machine is blown to the classifier by a fan, and after being screened and classified by the classifier, the qualified powder enters a bag filter for collection treatment, and large particles formed by agglomeration or adhesion of a modifier return to the primary activating machine and enter the activating treatment again;
step ten: and transferring the qualified powder collected by the bag filter to a finished product bin, discharging from the finished product bin, and packaging the finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310963113.0A CN116675994A (en) | 2023-08-02 | 2023-08-02 | High added value heavy calcium carbonate powder and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310963113.0A CN116675994A (en) | 2023-08-02 | 2023-08-02 | High added value heavy calcium carbonate powder and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116675994A true CN116675994A (en) | 2023-09-01 |
Family
ID=87785855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310963113.0A Pending CN116675994A (en) | 2023-08-02 | 2023-08-02 | High added value heavy calcium carbonate powder and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116675994A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467510A (en) * | 2013-09-29 | 2013-12-25 | 中国林业科学研究院林产化学工业研究所 | Preparing method of grease source silane coupling agent with toughening function |
| CN110484021A (en) * | 2019-08-07 | 2019-11-22 | 宜兴市涂门纳米新材料有限公司 | A kind of special cable special-purpose nanometer powdered whiting |
| CN113461725A (en) * | 2021-07-05 | 2021-10-01 | 浙江钦堂钙业有限公司 | Long-chain siloxane glyceride, blended calcium carbonate powder activator and preparation method |
| WO2023118361A1 (en) * | 2021-12-22 | 2023-06-29 | Omya International Ag | Precipitated calcium carbonate with high bio-based carbon content for polymer formulations |
-
2023
- 2023-08-02 CN CN202310963113.0A patent/CN116675994A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467510A (en) * | 2013-09-29 | 2013-12-25 | 中国林业科学研究院林产化学工业研究所 | Preparing method of grease source silane coupling agent with toughening function |
| CN110484021A (en) * | 2019-08-07 | 2019-11-22 | 宜兴市涂门纳米新材料有限公司 | A kind of special cable special-purpose nanometer powdered whiting |
| CN113461725A (en) * | 2021-07-05 | 2021-10-01 | 浙江钦堂钙业有限公司 | Long-chain siloxane glyceride, blended calcium carbonate powder activator and preparation method |
| WO2023118361A1 (en) * | 2021-12-22 | 2023-06-29 | Omya International Ag | Precipitated calcium carbonate with high bio-based carbon content for polymer formulations |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100348655C (en) | Preparation of polymer composite material from halloysite nanometer tube | |
| CN101914294B (en) | Paper-imitating biodegradable resin and preparation method | |
| CN1871289B (en) | Pvc-pcc nanocomposites resin composition with superior impact strengths and method for preparing the same | |
| JP4572516B2 (en) | Method for producing resin composition | |
| CN113248798B (en) | starch/cellulose/PBAT composite film and preparation method thereof | |
| CN106633722B (en) | Tear-resistant high-toughness biodegradable material and preparation method thereof | |
| CN110294923B (en) | Micro-foaming full-biodegradable polymer sheet and preparation method thereof | |
| CN111592667B (en) | Reinforced antibacterial artificial granite waste residue-based plastic master batch and preparation method thereof | |
| CN102702705A (en) | Toughened polylactic acid/polyolefin elastomer composite material and preparation method thereof | |
| CN112063022A (en) | Method for preparing waterproof starch-based degradable plastic master batch through mechanochemical modification | |
| CN102796294A (en) | Preparation method of calcium carbonate modified butylbenzene/natural rubber composite material | |
| CN113637299B (en) | Heat-resistant and impact-resistant polylactic acid composite material and preparation method and application thereof | |
| CN103374213A (en) | Preparation method of polylactic acid/montmorillonite nano composite material | |
| CN114507426A (en) | Modified nano calcium carbonate composite material and preparation method thereof | |
| CN102295831A (en) | Special material for fully biodegradable rigid sheet and preparation method thereof | |
| CN112358708A (en) | Biodegradable film blowing modified material with high starch content and preparation method thereof | |
| JP2007046019A (en) | Thermoplastic resin foam and method for producing the same | |
| JP2018070852A (en) | Resin composition | |
| CN116675994A (en) | High added value heavy calcium carbonate powder and production method thereof | |
| CN114921069B (en) | Full-biodegradable film with high heat seal strength and preparation method and application thereof | |
| Dorigato et al. | Effect of nanofillers addition on the compatibilization of polymer blends | |
| CN108841153A (en) | A kind of high-ductility, high heat distortion temperature poly (lactic acid) composition and preparation method thereof | |
| CN113462021B (en) | Natural filler, high-strength and high-toughness polymer composite material thereof, and preparation method and application thereof | |
| CN103965599A (en) | PLA (polylactic acid)/ABS (acrylonitrile-butadiene-styrene copolymers) alloy material and preparation method thereof | |
| CN114395139A (en) | Modified lignin suitable for fully-degradable membrane bags and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |