CN104370499B - A kind of preparation method of artificial red coral beading - Google Patents

A kind of preparation method of artificial red coral beading Download PDF

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Publication number
CN104370499B
CN104370499B CN201410509646.2A CN201410509646A CN104370499B CN 104370499 B CN104370499 B CN 104370499B CN 201410509646 A CN201410509646 A CN 201410509646A CN 104370499 B CN104370499 B CN 104370499B
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China
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red coral
powder
beading
coral
red
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Expired - Fee Related
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CN201410509646.2A
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CN104370499A (en
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彭秋明
吴文诗
李慧
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Yanshan University
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Yanshan University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone

Abstract

A kind of artificial red coral beading, its main component mass percent is: iron oxide red 5-20wt%, strontium carbonate 1-5wt%, unsaturated polyester type crystal resin 10-15wt%, and all the other are high-magnesian calcite; The preparation method of above-mentioned artificial red coral beading is by CaCl 2, MgCl 2, polyacrylic acid or poly-aspartate at reactor reaction 3-4 days, centrifugal drying obtains high-magnesian calcite powder; By strontium carbonate powder and high-magnesian calcite powder, FeCl 2put into water to stir respectively, then mix and blend 2-4h, ultrasonic 20min after adding ammoniacal liquor, 160-200 DEG C of reaction 12-24h in autoclave, centrifugal drying obtains red coral powder; Unsaturated polyester type crystal resin, red coral powder, curing agent and promoter are stirred 4-6h; Finally by casting, polishing, polishing, oil, obtain artificial red coral beading.Preparation method of the present invention and equipment simple, with short production cycle, be easy to large-scale production, the artificial red coral beading of preparation have the features such as uniform color, sparkling and crystal-clear bright and quality be fine and smooth.

Description

A kind of preparation method of artificial red coral beading
Technical field
The invention belongs to field of artware, particularly a kind of preparation method of red coral beading.
Background technology
Red coral was put in the middle of the wild animal of country-level focused protection in 1988.Red coral is grown in the deep-sea of 100 to 2000 meters away from the mankind, and neutral red coral is piled up by coral polyp to form, and growth is extremely slowly (one-inch needs long 20 to 30 years, one kilogram needs long 300 years), non-renewable.Red coral growth conditions is very harsh, and only between south, north latitude 30 degree, ocean current is steady, survives in the clean seawater that sunshine is moderate.Require that the depth of water, water are slow, without stormy waves interference, without cold and heat difference, long-term temperature almost constant 10 DEG C, therefore red coral is very rare.Red coral is mainly distributed in Mediterranean, marine site, Midway Island and marine site, Southeast Asia in the world.And the red coral of China is mainly distributed in the Taiwan Straits, and the only minority area survival such as in Lutao, Lanyu, little Ryukyu, Penghu.World today's red coral adopt the amount of obtaining every year between 100 tons to 400 tons, its price mostly is several times and even tens times of gold.In a lot of auction, the price of red coral works is also surprisingly high.Therefore red coral is also become " jewel coral " or " iris nobillis " by people.
Neutral red coral is so rare and expensive, and in order to meet the demand of Modern Decorative product, people have manufactured the artificial red coral of handicraft of imitative neutral red coral material and function thereof.Chinese invention patent application numbers 200710151119.9 discloses a kind of method preparing the artificial blue coral of health care, although the method has prepared blue beading with certain health care functions, but the actual constituent of this artificial blue coral and natural chemical composition differ larger, and preparation process is all adopt raw material mechanical agitation, so the artificial blue coral color and luster of preparation is uneven.
Document " " Guangxi science " 2000; 7 (4): 286-288.; " disclose a kind of method prepared hydro-thermal method and prepare synthetic ruby, the document utilizes water heat transfer ruby crystal, its crystal structure, chemical composition etc. are similar with natural ruby, but preparation process is unfavorable for industrialization to equipment requirement higher (high temperature, high pressure), production cycle length.
The major defect of existing technology of preparing is:
The first, service time longer easily appearance fades, falls the phenomenons such as slag.
The second, production process mechanical mixture is uneven, easily reunites, and causes final product color and luster uneven.
3rd, complicated process of preparation, high to equipment requirement, cost is higher, is not suitable for large-scale production simultaneously.
Summary of the invention
Object of the present invention is not only to provide that a kind of preparation technology is simple, uniform color, the preparation method of artificial red coral beading of not easily fading.
The main component mass percent of artificial red coral beading of the present invention is: iron oxide red 5-20wt%, strontium carbonate 1-5wt%, unsaturated polyester type crystal resin 10-15wt%, and all the other are high-magnesian calcite (content of magnesium 10-30mol%).
The preparation method of above-mentioned artificial red coral beading is as follows:
(1) high-magnesian calcite is prepared:
By 10mMCaCl 2and 1MMgCl 2volume ratio be 20-25:1, by CaCl 2and MgCl 2pour reactor into, then polyacrylic acid that molecular weight is 20k is added or molecular weight is 13.7k poly-aspartate, the polyacrylic acid wherein added or poly-aspartate concentration is in the reactor 10nM, cover after reactor reacts 3-4 days under room temperature, centrifugal drying obtains pure high-magnesian calcite powder;
(2) red coral powder is prepared:
The high-magnesian calcite powder adding 0.094-1.875g strontium carbonate powder and the above-mentioned preparation of 5.625-31.5g by often liter of water for industrial use mixes, then adds 3gFeCl by often liter of water for industrial use 2, by they respectively mechanical agitation 1-2h, then by the ratio mix and blend 2-4h of above-mentioned two kinds of solution 2:1 by volume, afterwards, by ultrasonic for above-mentioned mixed liquor 20min, pour in autoclave and react 12-24h at 160-200 DEG C, after centrifugal drying, red coral powder can be obtained;
(3) red coral beading are prepared:
In unsaturated polyester type crystal resin: red coral powder: curing agent (cyclohexanone peroxide): the ratio of the mass ratio=10-15:85-90:0.6-0.8:0.6-0.8 of promoter (cobalt naphthenate), unsaturated polyester type crystal resin, red coral powder and curing agent are stirred 4-6h under 500-1000r/min mixing speed; Poured into by the slurry mixed in the pearl type fiber reinforced plastic mold with cast gate and opening, wherein mould leaves a perforation line again.The rear 20-30min that crosses that cast opens mould, extracts perforation line out at once.The specification that the artificial red coral pearl base surface first polishing sanding of taking out from mould becomes to require, then at surface spraying one deck gloss oil, finally obtain red coral beading for color and luster excellence.
The present invention compared with prior art tool has the following advantages:
1, the artificial red coral beading uniform color of preparation, sparkling and crystal-clear bright;
2, artificial red coral beading for preparation not easily fade, fall slag, long service life;
3, preparation artificial red coral beading chemical composition and color and true red coral similarity high;
4, preparation process is simple, cost is low, environmentally friendly, with short production cycle, be applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the artificial red coral powder prepared before the embodiment of the present invention 1 does not add resin.
Fig. 2 is the pictorial diagram of the artificial red coral powder prepared before the embodiment of the present invention 2 does not add resin.
Fig. 3 is the pictorial diagram of the single pearl of artificial red coral prepared by the embodiment of the present invention 2.
Fig. 4 is the pictorial diagram of artificial red coral beading prepared by the embodiment of the present invention 3.
Detailed description of the invention
Embodiment 1
By 10mMCaCl 21000L and 1MMgCl 240L pours reactor into, then adds the polyacrylic acid that 208g molecular weight is 20k, and cover after reactor reacts 3 days under room temperature, centrifugal drying obtains pure high-magnesian calcite powder.Weigh strontium carbonate powder 15g is again added in the water for industrial use of 40L together with the high-magnesian calcite powder 1260g of above-mentioned preparation, 60gFeCl 2be dissolved in 20L water for industrial use, mechanical agitation 1h respectively, then by above-mentioned two kinds of solution mix and blend 2h, add 100ml ammoniacal liquor, ultrasonic 20min after mixing, pour in the autoclave of 100L and react 12h at 200 DEG C, red coral powder (as shown in Figure 1) after centrifugal drying, can be obtained; Unsaturated polyester type crystal resin 150g, above-mentioned red coral powder 1350g, cyclohexanone peroxide 12g and cobalt naphthenate 12g are stirred 4h under 500r/min mixing speed; The slurry mixed is poured in the pearl type fiber reinforced plastic mold with cast gate and opening, and wherein mould leaves a perforation line.The rear 20min that crosses that cast opens mould, carefully extracts perforation line out at once.The specification that the artificial red coral pearl base surface first polishing sanding of taking out from mould becomes to require, then at surface spraying one deck gloss oil, finally obtaining Strontium carbonate contents is 1wt%, iron oxide red content is 5wt%, unsaturated polyester type crystal resin content is 10wt%, and high-magnesian calcite (content of magnesium 10mol%) content is red coral beading of 84%.
Embodiment 2
By 10mMCaCl 21000L and 1MMgCl 250L pours reactor into, then adds the poly-aspartate that 144g molecular weight is 13.7k, and cover after reactor reacts 3 days under room temperature, centrifugal drying obtains pure high-magnesian calcite powder.Weigh strontium carbonate powder 22.5g is again added in the water for industrial use of 40L together with above-mentioned high-magnesian calcite powder 555g, 60gFeCl 2be dissolved in the water for industrial use of 20L, respectively mechanical agitation 1h, then by two kinds of solution mix and blend 3h, add 100ml ammoniacal liquor, ultrasonic 20min after mixing, pours in the autoclave of 100L and reacts 18h at 180 DEG C, can obtain red coral powder (as shown in Figure 2) after centrifugal drying; Unsaturated polyester type crystal resin 97.5g, above-mentioned red coral powder 652.5g, cyclohexanone peroxide 4.5g and cobalt naphthenate 4.5g are stirred 5h under 800r/min mixing speed; The slurry mixed is poured in the pearl type fiber reinforced plastic mold with cast gate and opening, and wherein mould leaves a perforation line.The rear 25min that crosses that cast opens mould, carefully extracts perforation line out at once.The specification that the artificial red coral pearl base surface first polishing sanding of taking out from mould becomes to require, then at surface spraying one deck gloss oil, finally obtain Strontium carbonate contents 3wt%, iron oxide red content is 10wt%, unsaturated polyester type crystal resin content is 13wt%, and high-magnesian calcite (content of magnesium 30mol%) content is red coral beading (as shown in Figure 3) of 74wt%.
Embodiment 3
By 10mMCaCl 21000L and 1MMgCl 250L pours reactor into, then adds the polyacrylic acid that 210g molecular weight is 20k, and cover after reactor reacts 4 days under room temperature, centrifugal drying obtains pure high-magnesian calcite powder.Weigh strontium carbonate powder 18.75g is again added in the water for industrial use of 40L together with the high-magnesian calcite powder 225g of above-mentioned preparation, 60gFeCl 2be dissolved in 20L water for industrial use, respectively mechanical agitation 2h, then both solution mix and blend 4h, add 100ml ammoniacal liquor, and ultrasonic 20min after mixing pours in the autoclave of 100L and reacts 24h at 200 DEG C, can obtain red coral powder after centrifugal drying; Unsaturated polyester type crystal resin 56.25g, red coral powder 318.75g, cyclohexanone peroxide 2.6g and cobalt naphthenate 2.6g are stirred 6h under 1000r/min mixing speed; The slurry mixed is poured in the pearl type fiber reinforced plastic mold with cast gate and opening, and wherein mould leaves a perforation line.The rear 30min that cast opens mould, carefully extracts perforation line out at once.The specification that the artificial red coral pearl base surface first polishing sanding of taking out from mould becomes to require, then at surface spraying one deck gloss oil, finally obtaining Strontium carbonate contents is 5wt%, iron oxide red content is 20wt%, unsaturated polyester type crystal resin content is 15wt%, and high-magnesian calcite (content of magnesium 30mol%) content is red coral beading (as shown in Figure 4) of 60wt%.
Embodiment 4
By 10mMCaCl 21000L and 1MMgCl 245L pours reactor into, then adds the poly-aspartate that 143.1g molecular weight is 13.7k, and cover after reactor reacts 4 days under room temperature, centrifugal drying obtains pure high-magnesian calcite powder.Weigh strontium carbonate powder 3.75g is again added in the water for industrial use of 40L together with the high-magnesian calcite powder 283.5g of above-mentioned preparation, 60gFeCl 2be dissolved in 20L water for industrial use, respectively mechanical agitation 2h, then both solution mix and blend 4h, add 100ml ammoniacal liquor, and ultrasonic 20min after mixing pours in the autoclave of 100L and reacts 24h at 200 DEG C, can obtain red coral powder after centrifugal drying; Unsaturated polyester type crystal resin 51.8g, red coral powder 318.2g, cyclohexanone peroxide 2.6g and cobalt naphthenate 2.6g are stirred 6h under 1000r/min mixing speed; The slurry mixed is poured in the pearl type fiber reinforced plastic mold with cast gate and opening, and wherein mould leaves a perforation line.The rear 30min that cast opens mould, carefully extracts perforation line out at once.The specification that the artificial red coral pearl base surface first polishing sanding of taking out from mould becomes to require, then at surface spraying one deck gloss oil, finally obtaining Strontium carbonate contents is 1wt%, iron oxide red content is 20wt%, unsaturated polyester type crystal resin content is 14wt%, and high-magnesian calcite (content of magnesium 15mol%) content is red coral beading of 65wt%.

Claims (2)

1. artificial red coral beading, it is characterized in that: its main component mass percent is: iron oxide red 5-20wt%, strontium carbonate 1-5wt%, unsaturated polyester type crystal resin 10-15wt%, all the other are high-magnesian calcite, and in described high-magnesian calcite, the content of magnesium is 10-30mol%.
2. the preparation method of a kind of artificial red coral beading according to claim 1, is characterized in that:
(1) high-magnesian calcite is prepared:
By 10mMCaCl 2and 1MMgCl 2volume ratio be 20-25:1, by CaCl 2and MgCl 2pour reactor into, then polyacrylic acid that molecular weight is 20k is added or molecular weight is 13.7k poly-aspartate, the polyacrylic acid wherein added or poly-aspartate concentration is in the reactor 10nM, cover after reactor reacts 3-4 days under room temperature, centrifugal drying obtains pure high-magnesian calcite powder;
(2) red coral powder is prepared:
The high-magnesian calcite powder adding 0.094-1.875g strontium carbonate powder and the above-mentioned preparation of 5.625-31.5g by often liter of water for industrial use mixes, then adds 3gFeCl by often liter of water for industrial use 2, by they respectively mechanical agitation 1-2h, then by the ratio mix and blend 2-4h of above-mentioned two kinds of solution 2:1 by volume, afterwards, by ultrasonic for above-mentioned mixed liquor 20min, pour in autoclave and react 12-24h at 160-200 DEG C, after centrifugal drying, red coral powder can be obtained;
(3) red coral beading are prepared:
In unsaturated polyester type crystal resin: red coral powder: curing agent cyclohexanone peroxide: the ratio of the mass ratio=10-15:85-90:0.6-0.8:0.6-0.8 of promoter cobalt naphthenate, unsaturated polyester type crystal resin, red coral powder, curing agent and promoter are stirred 4-6h under 500-1000r/min mixing speed; Poured into by the slurry mixed in the pearl type fiber reinforced plastic mold with cast gate and opening, wherein mould leaves a perforation line again; The rear 20-30min that crosses that cast opens mould, extracts perforation line out at once; The specification that the artificial red coral pearl base surface first polishing sanding of taking out from mould becomes to require, then at surface spraying one deck gloss oil, finally obtain red coral beading for color and luster excellence.
CN201410509646.2A 2014-09-28 2014-09-28 A kind of preparation method of artificial red coral beading Expired - Fee Related CN104370499B (en)

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JPH07170939A (en) * 1993-12-17 1995-07-11 Chiyougen Yamakawa Production of health enhancer
AU2007221771B2 (en) * 2000-11-16 2010-04-01 Biotomo Pty Ltd Processes for treating coral and coating an object
CN101461591A (en) * 2007-12-20 2009-06-24 天津市世纪东方建筑景观雕塑技术开发中心 Method for producing artificial blue coral bead with health-care function
CN101328039A (en) * 2008-08-04 2008-12-24 覃庆峰 Artificial stone panel and manufacturing method thereof
CN102907378B (en) * 2012-11-08 2014-02-12 石珠成 Cultivating method for ocean red corals

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