CN1763131A - Stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window - Google Patents
Stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window Download PDFInfo
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- CN1763131A CN1763131A CN 200510116792 CN200510116792A CN1763131A CN 1763131 A CN1763131 A CN 1763131A CN 200510116792 CN200510116792 CN 200510116792 CN 200510116792 A CN200510116792 A CN 200510116792A CN 1763131 A CN1763131 A CN 1763131A
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Abstract
The present invention is stearic acid modified nanometer calcium carbonate-PVC material for door and window. The present invention adopts nanometer particle to roughen and strengthen RPVC, high speed mixing and ultrasonic assisting to realize nanometer level dispersion of nanometer particle in polymer and to reach nanometer effect. The stearic acid modified nanometer calcium carbonate-PVC material consists of PVC 100 weight portions, composite stabilizer 3-8 weight portions, calcium carbonate 0-20 weight portions, titanium white powder 3-15 weight portions, stearic acid modified nanometer calcium carbonate 5-40 wt%, CPE 4-16 weight portions, machining assistant 0.1-5 weight portions and high temperature high efficiency flow modifier 0.01-5 weight portions. The material may be used in making window and door section in special shape and with high toughness and high rigidity.
Description
Technical field:
The present invention relates to a kind of stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window and manufacture method thereof.
Background technology:
Nano material and technology become the field, forefront of modern science and technology just day by day.Utilize nano inorganic material to carry out modification, thereby increase substantially the performance such as intensity, rigidity, thermotolerance of matrix material, for the high performance of macromolecular material provides a valid approach macromolecular material.Polyvinyl chloride (PVC) is a kind of widely used plastics, particularly hard PVC＜RPVC〉in the chemical building material field, use increasingly extensive, as the RPVC plastic-steel door and window, RPVC building pipe etc.But also there are some fatal defectives in RPVC, and particularly property is crisp, shock strength is low, if toughness reinforcing to it without elastomerics, then has no value for use.Past, general chlorinatedpolyethylene (CPE) or the EVA of adopting carried out toughening modifying to it, but after adopting CPE or EVA to the RPVC toughening modifying, its rigidity, thermotolerance, hardness descend significantly, thereby make RPVC yielding, the easy scuffing in surface etc., prepared door and window anti-wind pressure descends, and stopping property descends.So must improve at this shortcoming.Nano material can reach not only toughness reinforcing but also not reduce the inflexible effect the RPVC modification.The present invention adopts nano-calcium carbonate exactly, and to its surface with stearic acid carry out special processing toughness reinforcing so that RPVC is played, strengthen, increase firm effect.
The impact modifying agent of using in the current PVC goods is CPE, EVA, MBS and ACR etc., the problem that exists rigidity and toughness not to take into account, toughness has improved often, but tensile strength, rigidity and hardness, thermotolerance descend significantly, cause dimensional stability bad, yielding.Nanoparticle＜inorganic and organic filler〉there is toughness reinforcing enhancing to increase firm effect to polymkeric substance, utilize these characteristics of nanoparticle to carry out modification to macromolecular material, have high tenacity high inflexible elite clone is arranged again thereby make.But common nano-powder is difficult to reach the nano-dispersed in polymeric matrix, thereby can not embody nano effect.The invention reside in and realize that nanoparticle increases firm effect to the toughness reinforcing enhancing of RPVC, adopt high-speed mixing and ultrasonic auxiliary, make nanoparticle in polymeric matrix, reach nano-dispersed, fully represent nano effect.
Summary of the invention:
The redigity impact modifying agent that the present invention is prepared, it is characterized in that: contain 5～30%＜weight〉stearic acid modified nano-calcium carbonate, this properties-correcting agent can make inorganic nano-particle fully be distributed in the matrix resin, give full play to the nanoparticle effect, make inorganic with organically rigidity and toughness organically combine.
Nano-calcium carbonate that the present invention adopts is to be the nano-calcium carbonate (CaCO that properties-correcting agent carries out surface modification with the stearic acid
3), its size of particles is 10～100nm, preferred 20～60nm.
The present invention adopts the high-speed mixing of nanoparticle to disperse and ultrasonic aid dispersion.High-speed mixing of the present invention is produced used high-speed mixer for the PVC section bar.
The preparation method of nano redigity impact modifying agent of the present invention follows these steps to carry out:
1, the butyl acrylate of 10-70% (weight), the ethyl propenoate of 10-30% (weight), the vinylbenzene of 0-50% (weight) are put into the reactor that is added with emulsifying agent, add quantitative deionized water, in 40～70 ℃, preferred 50～60 ℃ of fully stirrings down, make it complete emulsification.
2, in room temperature～100 ℃ nano inoganic particle that preferred 50～80 ℃ of following addings are dissolved with emulsifying agent, surface-modifying agent in advance in deionized water, under the ultrasonic wave effect 5～120 minutes, preferred 10～60 minutes, more preferably 20～40 minutes.
3, with (1) and (2) thorough mixing, make it to be warming up to 50～90 ℃, preferred 60～80 ℃, add the good initiator of dissolving in advance, under this temperature, reacted preferred 2～3 hours 1～5 hour.
4, add initiator solution, under this temperature, drip methyl methacrylate, added in 0.5～3 hour, preferred 1～2 hour.
5, heat up 80～96 ℃, preferred 85～90 ℃, slaking 0.5～3 hour, F made nano-composite emulsion in preferred 1～2 hour.
6, carry out drying among nano-composite emulsion being joined the hig h-speed centrifugal spray drying device, make Powdered nano redigity impact modifying agent; Or nano-composite emulsion is slowly put in the lead sulfate solution or calcium chloride solution of 0.5～5 (weight) % concentration, stir the breakdown of emulsion cohesion after, filter, wash three times after, in 50～60 ℃ of following vacuum-dryings.
The prepared nano redigity impact modifying agent of the present invention has nuclear--shell structure, can carry out good mixing with PVC, and embody nano effect.
Section bar of the present invention specifically consists of: PVC 100 weight parts; One package stabilizer 3～8 weight parts, preferred 4～6 weight parts; Lime carbonate 0～20 weight part, preferred 6～15 weight parts, most preferably 6～10 weight parts; Titanium dioxide 3～15 weight parts, preferred 4～10 weight parts; The CPE4-16 weight part, preferred 8～12 weight parts; Nano-calcium carbonate 5～40 weight parts, preferred 10～25 weight parts; High temperature high efficiency flow properties-correcting agent 0.01～5 weight part, preferred 0.3～1 weight part; Processing aid 0.1～5 weight part, preferred 0.5～1 weight part.
The polyvinyl chloride resin that the present invention uses, its K value is 63～72L/g, SG-5, the SG-6 type of S-900 type, S-1000 type, S-1100 type or Beijing chemical industry two factories of preferred Qilu Petrochemical company.
The nano-calcium carbonate that the present invention uses must carry out surface modification with stearic acid after moulding, to avoid agglomeration, used particle diameter is 20～100nm, preferred 40～60nm.
The one package stabilizer that the present invention uses, it consists of: the organic lead plumbate 50～80% (weight) except that lead stearate, preferred 60～70% (weight); Paraffin 5～20% (weight), preferred 6～10% (weight); Lead stearate 10～20%＜weight 〉, preferred 15～18% (weight); Polyol ester 0.1～10% (weight), preferred 3～5% (weight); Used organic lead plumbate is a kind of or its mixture of fumaric acid lead, phthalic acid lead and chloriduria lead plumbate.
The high temperature high efficiency flow properties-correcting agent that the present invention uses is oxidized polyethlene wax, and its molecular weight is 1000～100000, preferred 3000～10000, its softening temperature is 85 ℃～120 ℃, preferred 100～115 ℃, preferably use U.S. Intertrust, Inc. (Allied SignalCO., A-C307A Ltd).
The processing aid that the present invention uses is a kind of auxiliary agent that can promote the PVC fusion plastification, is acrylic polymer, or esters of acrylic acid and cinnamic multipolymer.Select a kind of or above-mentioned several mixture of ACR-201 (Amway chemical plant, Suzhou or coral monkey chemical plant, Shanghai), ACR-401 (Amway chemical plant, Suzhou or Shanghai Shanhu Chemical Factory, Shanghai), M-80 (security personnel chemical plant, Wu County, Jiangsu) and K-125P (Japanese KurehaChemicals[Singapore] PTE-Ltd. or U.S. Rohm-Haas company) for use.
Lime carbonate (the CaCO that the present invention uses
3) be lightweight CaCO
3, colloid CaCO
3, active light CaCO
3, heavy CaCO
3With active CaCO
3A kind of or above-mentioned several mixture, preferred active light CaCO
3
The iron white powder that the present invention uses is characterized by rutile-type, a kind of or its mixture of the N 2 2220 of the R-960 of preferred Dupont (DuPont) company and German Kronos company.
The present invention is compound by using N-ACR and other auxiliary agent to carry out, thereby makes formed nano-PVC composition have the excellent comprehensive performance, has reached not only to have increased just but also toughness reinforcing purpose.
Embodiment:
Be described further below in conjunction with specific embodiment, the umber described in the application's book is parts by weight, unless stated otherwise.
Embodiment 1, take by weighing 10 weight part (weight, nano-calcium carbonate (particle diameter 20～40nm) down together), 4 weight part sodium lauryl sulphate (SDS), 1 weight part sodium polyacrylate, 280 parts by weight of deionized water join in the 500ml four-hole boiling flask, stir, put into water-bath simultaneously, be warming up to 68 ℃, start the ultrasonic wave effect after 30 minutes, add 40 weight part BA, 10 weight part EA, 0.2 weight part dimethacrylate macrogol ester, high degree of agitation 10 minutes, treat that temperature reaches 68 ℃ after, add the aqueous solution of Potassium Persulphate, concentration is 5% (weight).Temperature remains in 65～70 ℃ of scopes, reacts after 2 hours, drips the MMA40 weight part, dropwises in 1.5～2 hours.Be warming up to 85～90 ℃, react after 1 hour, made emulsion is put in 3% (weight) aluminum sulfate aqueous solution of 90 ℃, breakdown of emulsion, cohesion is filtered, after washing three times, put into vacuum drying oven, promptly make nano redigity impact modifying agent in 50～60 ℃ times dry 4～6 hours.No grumeleuse, breakdown of emulsion and precipitation after letex polymerization finishes.
Embodiment 2, take by weighing 20 weight part nano-calcium carbonates (particle diameter 30～60nm), 3 weight part Sodium dodecylbenzene sulfonatees, 2 weight part AP-1 (Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing's product), 280 parts by weight of deionized water join in the 500ml four-hole boiling flask, put into water-bath, be warming up to 72 ℃, stir, and place the ultrasonic wave field effect after 15 minutes, add 40 weight part BA, stir after 10 minutes, adding 10ml concentration is the persulfate aqueous solution of 5% (weight), and reflux condensation mode reacted 4 hours.Add 0.1 weight part dibenzoyl peroxide and 10 parts by weight of styrene then, react after 2 hours, adding 4ml concentration is the persulfate aqueous solution of 5% (weight), stir after 5 minutes, from drip pipe, drip 20 weight part MMA, in 1～2 hour, dropwise, react after 1 hour, be warming up to 85 ℃, slaking 1 hour is slowly put into the gained emulsion in 3% (weight) calcium chloride water of 90 ℃ then, stir, breakdown of emulsion cohesion is filtered, wash three times after, in 50～60 ℃ of following vacuum-dryings 4～6 hours, pulverize, cross 80 mesh sieves, promptly get Powdered nano redigity impact modifying agent.
Embodiment 3, take by weighing 120 weight part nano-calcium carbonate (particle diameters 20～40nm), 8 weight part sodium lauryl sulphate (SDS), 8 weight part MS-1,4 weight part sodium polyacrylates, 1120 parts by weight of deionized water, 1.2 weight part titanate coupling agent, put in the 200oml four-hole boiling flask, this flask is put into ultrasound bath, heat up and stir, and start ultrasonic wave, after acting on 30 minutes under 70 ℃, add 120 weight part BA, stir after 10 minutes, adding 24ml concentration is the persulfate aqueous solution of 5% (weight), react after 2 hours, add the persulfate aqueous solution that 24ml concentration is 5% (weight) again, drip monomer mixture 160 weight parts contain MMA and St (MMA: St=80 wherein: 20), in 1～2 hour, dropwise then.Be warming up to 85 ℃, react after 2 hours, be cooled to room temperature, adopt spray-dryer to be drying to obtain Powdered nano redigity impact modifying agent at last.
Claims (3)
1, a kind of stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window, it is characterized in that: it contains the PVC100 weight part, one package stabilizer 3～8 weight parts, lime carbonate 0～20 weight part, white powder 3～15 weight parts of admiring, stearic acid modified nano-calcium carbonate 5～40 weight parts, the CPE4-16 weight part, processing aid 0.1～5 weight part, high temperature high efficiency flow properties-correcting agent 0.01～5 weight part, wherein, used one package stabilizer contains organic lead plumbate 50～80 weight % except that hard lead acid based on the weight of this one package stabilizer, paraffin 5～20 weight %, lead stearate 10～20 weight %, polynary alcoholase 0.1～10 weight %; Used processing aid is vinylformic acid enzyme or esters of acrylic acid and cinnamic multipolymer; Used high temperature high efficiency flow properties-correcting agent is the oxidized polyethlene wax class; Used stearic acid modified nano-calcium carbonate, size of particles are 20～60nm.
2, according to right 1 described stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window, it is characterized in that: the K value of used PVC is 63～72mL/g, and used titanium dioxide is a rutile-type, used lime carbonate is lightweight, or the lightweight activity, or heavy, or heavy activity, or colloid CaCO
3
3, a kind of preparation method of stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window is characterized in that: comprise the step of extruding claim 1 or 2 described PVC compositions by taper or parallel double-screw extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510116792 CN1763131A (en) | 2005-11-01 | 2005-11-01 | Stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window |
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|---|---|---|---|
| CN 200510116792 CN1763131A (en) | 2005-11-01 | 2005-11-01 | Stearic acid modified nanometer calcium carbonate PVC isosection bar for door and window |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061044A (en) * | 2010-12-10 | 2011-05-18 | 河南理工大学 | High shock resistance type inflaming retarding antistatic polyvinyl chloride composition and preparation method thereof |
| CN101775180B (en) * | 2009-12-29 | 2012-06-20 | 山东华信塑胶股份有限公司 | Impact-resistant modified polyvinyl chloride tube material and preparation process thereof |
| CN102942754A (en) * | 2012-12-07 | 2013-02-27 | 山东博拓塑业股份有限公司 | High-hardness polyvinyl chloride free foaming plate material and preparation method of same |
| CN102977498A (en) * | 2012-12-04 | 2013-03-20 | 安徽康嘉塑胶建材有限公司 | Polyvinyl chloride (PVC) composite electrical sleeve |
| CN103613844A (en) * | 2013-11-20 | 2014-03-05 | 上海琥达投资发展有限公司 | Energy-conserving, environment-friendly and recyclable thermosetting resin composite material and application thereof |
| CN103694602A (en) * | 2013-12-14 | 2014-04-02 | 苏州戴尔曼电器有限公司 | Polyvinyl chloride composite electrical casing |
| CN109968775A (en) * | 2019-04-10 | 2019-07-05 | 大连路安建材有限公司 | A kind of compound antiglare shield of Nano self-cleaning PVC |
| CN117164959A (en) * | 2023-09-04 | 2023-12-05 | 福建联塑新材料科技有限公司 | Modified nano calcium carbonate, modified PVC resin and application thereof |
| CN117164959B (en) * | 2023-09-04 | 2024-10-22 | 福建联塑新材料科技有限公司 | Modified nano calcium carbonate, modified PVC resin and application thereof |
-
2005
- 2005-11-01 CN CN 200510116792 patent/CN1763131A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775180B (en) * | 2009-12-29 | 2012-06-20 | 山东华信塑胶股份有限公司 | Impact-resistant modified polyvinyl chloride tube material and preparation process thereof |
| CN102061044A (en) * | 2010-12-10 | 2011-05-18 | 河南理工大学 | High shock resistance type inflaming retarding antistatic polyvinyl chloride composition and preparation method thereof |
| CN102977498A (en) * | 2012-12-04 | 2013-03-20 | 安徽康嘉塑胶建材有限公司 | Polyvinyl chloride (PVC) composite electrical sleeve |
| CN102942754A (en) * | 2012-12-07 | 2013-02-27 | 山东博拓塑业股份有限公司 | High-hardness polyvinyl chloride free foaming plate material and preparation method of same |
| CN102942754B (en) * | 2012-12-07 | 2015-06-10 | 山东博拓塑业股份有限公司 | High-hardness polyvinyl chloride free foaming plate material and preparation method of same |
| CN103613844A (en) * | 2013-11-20 | 2014-03-05 | 上海琥达投资发展有限公司 | Energy-conserving, environment-friendly and recyclable thermosetting resin composite material and application thereof |
| CN103694602A (en) * | 2013-12-14 | 2014-04-02 | 苏州戴尔曼电器有限公司 | Polyvinyl chloride composite electrical casing |
| CN109968775A (en) * | 2019-04-10 | 2019-07-05 | 大连路安建材有限公司 | A kind of compound antiglare shield of Nano self-cleaning PVC |
| CN117164959A (en) * | 2023-09-04 | 2023-12-05 | 福建联塑新材料科技有限公司 | Modified nano calcium carbonate, modified PVC resin and application thereof |
| CN117164959B (en) * | 2023-09-04 | 2024-10-22 | 福建联塑新材料科技有限公司 | Modified nano calcium carbonate, modified PVC resin and application thereof |
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