CN1121445C - Nano PVC door and window profile material composition - Google Patents
Nano PVC door and window profile material composition Download PDFInfo
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- CN1121445C CN1121445C CN 00134588 CN00134588A CN1121445C CN 1121445 C CN1121445 C CN 1121445C CN 00134588 CN00134588 CN 00134588 CN 00134588 A CN00134588 A CN 00134588A CN 1121445 C CN1121445 C CN 1121445C
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Abstract
The present invention provides a PVC composition of a rigid impact modifying agent containing a nanometer core-shell structure. The present invention is characterized in that the PVC composition contains the following raw materials by the weight portion: 100 portions of PVC, 3 to 8 portions of composite stabilizing agent, 5 to 30 portions of calcium carbonate, 3 to 25 portions of white titanium powder, 2 to 30 portions of rigid impact modifying agent containing a nanometer core-shell structure(called N-ACR in the following part), 0.1 to 5 portions of auxiliary processing agent and 0.01 to 5 portions of high-temperature high-efficiency flow modifying agent.
Description
Technical field
The present invention relates to a kind of composition of nano-PVC, be used to prepare the hard PVC door and window profile material.
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 that a kind of widely used plastics, particularly hard PVC (RPVC) are used in the chemical building material field increasingly extensive, as the RPVC plastic-steel door and window, and 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 inoganic particle exactly, and to its carry out special processing make compound redigity impact modifying agent (N-ACR) with nuclear-shell structure to RPVC carry out toughness reinforcing, strengthen, increase just.
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) has toughness reinforcing enhancing to increase firm effect to polymkeric substance, utilizes these characteristics of nanoparticle to carry out modification to macromolecular material, has 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 ultrasonic auxiliary and in-situ polymerization, 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: the nano inoganic particle that contains 5～95% (weight), preferred 20～40% (weight), the polymkeric substance of 5～95% (weight), preferred 60～80% (weight), this properties-correcting agent has nuclear-shell structure, 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 inoganic particle of the present invention is one of following or its mixture: nano silicon (SiO
2), nano silicon-based oxide (SiO
2-x), nano-calcium carbonate (CaCO
3), super-fine talc, ultra-fine barium sulfate, super fine alumina, nano titanium oxide, its size of particles is 10～100nm, preferred 20～60nm.
The present invention adopts the ultrasonic aid dispersion and the in-situ emulsion polymerization of nanoparticle.The initiator of in-situ emulsion polymerization of the present invention is a kind of or its mixture of Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, emulsifying agent is a kind of or its mixture of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, MS-1, tween-80, active modifier is the poly carboxylic acid sodio-derivative, linking agent is a Vinylstyrene, a kind of or its mixture of dimethacrylate Tetraglycol 99 ester, Ethylene glycol dimethacrylate, dimethacrylate macrogol ester.
Polymkeric substance of the present invention is following monomeric multipolymer: (a) butyl acrylate of 10～70% (weight); (b) methyl methacrylate of 10～60% (weight); (c) ethyl propenoate of 10～30% (weight); (d) vinylbenzene of 0～50% (weight); (e) the vinylformic acid initiator of 0～20% (weight).
Letex polymerization of the present invention, the emulsification dosage of its use is 0.1～10% (weight), preferred 2～6% (weight), active modifier is 0.01～5% (weight), preferred 0.5～3% (weight), more preferably 1～2% (weight), linking agent is 0.1～5% (weight), preferred 1～2% (weight).
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.
In room temperature～100 ℃, preferred 50～80 ℃ of following addings be dissolved with emulsifying agent, surface-modifying agent in advance nano inoganic particle 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 preferred 1～2 hour, makes nano-composite emulsion.
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, embodies nano effect.
The composition of nano-PVC 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 5～30 weight parts, preferred 6～20 weight parts,
Preferred 6～10 weight parts
Titanium dioxide 3～25 weight parts, preferred 4～10 weight parts
N-ACR 2～30 weight parts, preferred 8～12 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 63～72mL/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 N-ACR that the present invention uses, its constitutional features is for having nuclear-shell structure, and it contains: the nano inoganic particle of 5～95% (weight), preferred 10～30% (weight); The superpolymer of 5～95% (weight), preferred 70～90% (weight).Employed nano inoganic particle is SiO
2, CaCO
3, talcum powder, kaolin, BaSO
4Deng, preferred SiO
2, CaCO
3, used particle diameter is 20～100nm, preferred 40～60nm.Its detailed preparation is applied for a patent simultaneously.
The one package stabilizer that the present invention uses, it consists of:
Except that lead stearate
Organic lead plumbate 50～80% (weight), 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 cyanogen urea 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 Signal Co., 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 Shanghai Shanhu Chemical Factory, 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 calcene.
The titanium dioxide that the present invention uses is characterized by rutile-type, a kind of or its mixture of the N-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 further described 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 silicon (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 silicon-based oxide (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 2000ml 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.
Embodiment 4 and Comparative Examples 1
In the present embodiment, the nano-PVC composition that is adopted consists of (weight parts by weight, down together):
Embodiment 4 Comparative Examples 1
PVC (SG-5 type, Beijing chemical industry two factories), 100 100
One package stabilizer 55
Lightweight CaCO
355
Titanium dioxide (N-2220) 55
N-ACR (nano redigity impact modifying agent) 80
Processing aid 0.5 2
A-C307A 0.01
Technical process is: by the prescription weighing good after, drop in the high-speed mixer, rotating speed 1400～2000rpm, relying on rubs makes it be warming up to 110～120 ℃, after discharging is cooled to 40 ℃, standby.Start double roll mill, be warming up to 160～180 ℃.The above-mentioned material that mixes joined between two rollers open refining, slice after 5～15 minutes time, the about 0.5mm of thickness is cut into the sheet of about 150mm * 150mm, stack 10～15 layers, put into vulcanizing press, be heated to 160～180 ℃, be forced into 10～15MPa, keep 10～15min postcooling, to be cooled to the taking-up of back below 40 ℃, gauge control is carried out the sample preparation test with omnipotent sampling machine between 4～6mm.
Test result sees Table 1.
Table 1 embodiment 4 and Comparative Examples 1 The performance test results
Annotate: * adopts two-sided v-notch to test.Continuous table 1
| Tensile strength elongation at break shock strength *Low temperature impact strength * (GB/T1040-92) (GB/T1040-92) (ISO179：1993) (ISO179：1993) | |
| Comparative Examples 1 | 68 15 5.8 3.5 |
| Embodiment 4 | 62 77 22.2 11.6 |
| Flexural strength bending elastic modulus Vicat softening point hardness (Rockwell hardness) | |
| (GB/T9341-88) (GB/T9341-88) (GB/T1633-79) (GB/T9342-88) | |
| Comparative Examples 1 | 75.2 2724.3 93 82 |
| Embodiment 4 | 79.8 2701.6 95 83 |
As can be seen from Table 1,, make the shock strength (comprising low temperature impact strength) of RPVC obtain increasing substantially, kept the original rigidity of RPVC, thermotolerance, hardness and intensity simultaneously by adding N-ACR, have significantly toughness reinforcing, strengthen and increase firm effect.
Embodiment 5 and Comparative Examples 2:
In the present embodiment, the nano-PVC composition that is adopted consists of:
Embodiment 5 Comparative Examples 2
PVC (S-1000 type, Qilu Petrochemical) 100 100
One package stabilizer 45
CaCO
3(activity, heavy) 66
Titanium dioxide 44
N-ACR 10
CPE 10
ACR-201 0.5 2
A-C307A 0.3 0.5
Preparation technology is with embodiment 4.Test result sees Table 2.
The performance of table 2 embodiment 5 and Comparative Examples 2 (testing method is with table 1)
Continuous table 2
| Tensile strength elongation at break shock strength low temperature impact strength | |
| (MPa) (%) (two V breach, KJ/m 2) (two V breach, KI/m 2) | |
| Comparative Examples 2 | 45 89 32 15 |
| Embodiment 5 | 67 68.8 28 13.8 |
| Flexural strength bending elastic modulus Vicat softening point hardness | |
| (MPa) (MPa) (℃) (Rockwell hardness) | |
| Comparative Examples 2 | 66 2002.6 86 72 |
| Embodiment 5 | 82 2511.3 93 84 |
As can be seen from Table 2, embodiment 5 adopts 10 weight part N-ACR modifications, and Comparative Examples 2 is to adopt 10 weight part CPE modifications.The two performance is compared, embodiments of the invention 5 have more excellent comprehensive performance, it has kept the original rigidity of RPVC, hardness and thermotolerance in toughness reinforcing: and the CPE modified system, its shock strength is higher, but it is very big that intensity and rigidity, hardness are lost, and lost the lot of valuable performance of RPVC.So the present invention has more excellent comprehensive performance.
Embodiment 6 and Comparative Examples 3
In the present embodiment, the nano-PVC composition that is adopted, it consists of:
Embodiment 6 Comparative Examples 3
PVC (S-1100, Qilu Petroleum Chemical Corporation Institute) 100 100
One package stabilizer 66
Calcene 88
Titanium dioxide (R-902 of Du Pont) 6 6N-ACR 8EVA (VA content 26%) 10ACR-401 0.5 2 preparation technologies are with embodiment 4.Results of property sees Table 3.
The performance of table 3 embodiment 6 and Comparative Examples 3
Continuous table 3
| Tensile strength elongation at break shock strength low temperature impact strength | |
| (MPa) (%) (two V breach, KJ/m 2) (two V breach, KI/m 2) | |
| Comparative Examples 3 | 68 78 25.8 13.9 |
| Embodiment 6 | 42 95 30.2 12.6 |
| Flexural strength bending elastic modulus Vicat softening point hardness | |
| (MPa) (MPa) (℃) (Rockwell hardness) | |
| Comparative Examples 3 | 82 2491 92 85 |
| Embodiment 6 | 61 1936 85 70 |
As can be seen from Table 3, nano redigity impact modifying agent of the present invention and EVA contrast have higher shock strength, tensile strength and modulus value, show to have comprehensive performance.
Claims (3)
1. PVC composition that contains the redigity impact modifying agent of nano core-shell structure, it is characterized in that: it contains the PVC100 weight part, one package stabilizer 3～8 weight parts, lime carbonate 5～30 weight parts, titanium dioxide 3～25 weight parts, nano core-shell structure rigidity impact modifying agent 2～30 weight parts, 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, paraffin 5～20 weight %, lead stearate 10～20 weight %, polyol ester 0.1～10 weight % based on the weight of this one package stabilizer;
Used processing aid is esters of acrylic acid or esters of acrylic acid and cinnamic multipolymer;
Used high temperature high efficiency flow properties-correcting agent is the oxidized polyethlene wax class;
Used nano core-shell structure rigidity impact modifying agent consists of nano inoganic particle 5～95 weight %, superpolymer 5～95 weight % based on the gross weight of this nano core-shell structure rigidity impact modifying agent; Wherein, described superpolymer contains the butyl polyacrylate of 10～70 weight %, the polymethylmethacrylate of 10～50 weight %, the polystyrene of the polyethyl acrylate of 10～30 weight % and 10～50 weight % based on the gross weight of this superpolymer; Described nano inoganic particle is a kind of or its mixture in nano silicon, nano silicon-based oxide, nano-calcium carbonate, super-fine talc, ultra-fine barium sulfate, super fine alumina, the nano titanium oxide, and its size of particles is 40～60nm.
2. according to right 1 described PVC composition, the K value that it is characterized in that used PVC is 63～72mL/g, and used titanium dioxide is a rutile-type, and used lime carbonate is lightweight, or the lightweight activity, or heavy, or the heavy activity, or colloid CaCO
3
3. the preparation method of a nanometer section bar comprises the step of extruding claim 1 or 2 described PVC compositions by taper or parallel double-screw extruder.
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|---|---|---|---|
| CN 00134588 CN1121445C (en) | 2000-12-12 | 2000-12-12 | Nano PVC door and window profile material composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00134588 CN1121445C (en) | 2000-12-12 | 2000-12-12 | Nano PVC door and window profile material composition |
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|---|---|
| CN1358795A CN1358795A (en) | 2002-07-17 |
| CN1121445C true CN1121445C (en) | 2003-09-17 |
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| CN101514247B (en) * | 2009-03-01 | 2011-04-13 | 大连天元精细化工有限公司 | High-efficiency multifunctional compound enforcing agent and preparation method 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 |
| CN102352077A (en) * | 2011-07-07 | 2012-02-15 | 鹤山联塑实业发展有限公司 | Environment-friendly aging-resistant polyvinyl chloride (PVC) section |
| CN103509272A (en) * | 2012-06-20 | 2014-01-15 | 马平芳 | Hard multifunctional PVC assistant |
| CN103122111B (en) * | 2013-02-27 | 2015-05-13 | 东莞欧德雅装饰材料有限公司 | Environment-friendly PVC (polyvinyl chloride) household edge banding and preparation method thereof |
| CN104130525B (en) * | 2014-07-31 | 2016-09-28 | 河南联塑实业有限公司 | A kind of low temperature toughening PVC drain pipe material and its preparation method and application |
| CN104277382A (en) * | 2014-11-07 | 2015-01-14 | 安徽省三乐门窗幕墙工程有限公司 | Antifouling heat preservation door and window plastic steel profile and preparation method thereof |
| CN104479239A (en) * | 2014-11-07 | 2015-04-01 | 安徽省三乐门窗幕墙工程有限公司 | Antioxidation door-window plastic-steel section material and preparation method thereof |
| CN104479259A (en) * | 2015-01-21 | 2015-04-01 | 芜湖海螺型材科技股份有限公司 | High-impact-resistance PVC profile meeting high-speed extrusion requirement and preparing method thereof |
| WO2017222483A1 (en) * | 2016-06-23 | 2017-12-28 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | A cost-effective impact resistance-increasing hybrid composite material and a production method thereof |
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| CN107226970A (en) * | 2017-05-24 | 2017-10-03 | 周建华 | Nano composite material and preparation method thereof |
| CN109648926B (en) * | 2018-12-21 | 2024-05-03 | 河北广通塑胶管道工程有限公司 | PVC (polyvinyl chloride) plate, preparation method and application thereof in manufacturing pipeline room |
| CN111073178A (en) * | 2019-12-30 | 2020-04-28 | 山东霞光集团有限公司 | Plastic steel profile and preparation method thereof |
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