CN105001623A - Solution method-based method for preparing polyurethane alloy - Google Patents
Solution method-based method for preparing polyurethane alloy Download PDFInfo
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- CN105001623A CN105001623A CN201510426214.XA CN201510426214A CN105001623A CN 105001623 A CN105001623 A CN 105001623A CN 201510426214 A CN201510426214 A CN 201510426214A CN 105001623 A CN105001623 A CN 105001623A
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Abstract
The invention relates to a solution method-based method for preparing polyurethane alloy. According to the method, 10-100 parts of unsaturated monomers and 100 parts of polyol are subjected to the prepolymerization process at 60 to 80 DEG C for 0.5 to 2 hours, wherein an initiator for free radical polymerization are dissolved in the unsaturated monomers and a catalyst is dissolved in the polyol. After that, a solvent is added in the above mixture and the obtained product is stirred evenly. Then the metered isocyanate and a chain extender are added for further reaction at 80 to 100 DEG C for 1 to 10 hours to obtain a polyurethane alloy solution. After that, the polyurethane alloy solution is added in water, so that the blocky polyurethane alloy is enabled to dissolve out. The blocky polyurethane alloy is crushed into particles and then dried at 130 DEG C for 3-8 hours to obtain the polyurethane alloy particle material. The method is simple in preparation process and polymers are blended at the molecular level. The problem that the polyurethane and the polyolefin are poor in mixing compatibility can be solved. The obtained polyurethane alloy is good in toughness, excellent in strength and high in modulus.
Description
Technical field
The invention belongs to polymer-function material field, be specifically related to a kind of method that solution method prepares polyurethane alloys.
Background technology
Thermoplastic elastomer is the so-called third generation rubber after natural rubber, synthetic rubber, and be often called as thermoplastic elastomer, have toughness and elasticity under room temperature, it at high temperature has mobility, can plasticizing forming.Thermoplastic elastomer molecular chain structure comprises hard section and soft section, and wherein hard section part shows plastic working characteristic; Soft section of part is made decision as its rubber segments normal temperature the elasticity of thermoplastic elastomer.Because thermoplastic elastomers is for the dual nature of rubber and plastics, so can be used for rubber overshoes, tackiness agent, automobile component, electric wire, sebific duct, coating etc.Relate to the various fields such as automobile, electric wire, sports goods, building materials, electron device, leather, sealing member, power tool, IT industry, toy.Thermoplastic elastomer developed rapidly in recent years, was the product of state key encourage growth.
Thermoplastic polyurethane (be called for short TPU) is the important thermoplastic elastic material of a class, integrates the macromolecular material of the snappiness of rubber and the molding processibility of thermoplastics simultaneously.In molecular structure, the existence of a large amount of hydrogen bond is polyurethane elastomer significant structural performance.The polar group contained in the molecular structure of TPU, under hydrogen bond action, makes carbamate groups flock together and forms hard section; And nonpolar ether and ester group flock together and form soft section under same effect.Hard section is containing the strong group of polarity, and mutual magnetism is large, and soft section of difference produced to result on thermodynamics incompatible, therefore hard section easily flocks together formation microcell, be distributed in soft section mutually in, be referred to as " microphase-separated ".This feature makes that TPU has good elasticity, machinery is forced the way across, oil resistant, ozone resistance, excellent low-temperature performance etc.; But its shortcoming is quite a few, mainly comprises: ageing resistance is poor, low, the easy skidding of poor fire, wet structure frictional coefficient, poor processability, cost are more high.Therefore, the polymkeric substance with different performance is prepared into polymer alloy by blending and modifying, can obtains single polymers does not have or better properties, the research of its theory and practice is in recent years very active, and achieves some important progress.
Technology For Polymer Alloy is utilized to prepare polyurethane alloys, the physical property of some excellences of TPU can be utilized to improve the deficiency of some other polymer performance aspect on the one hand, also the specific performance of other polymkeric substance can be adopted to the defect in some performance making up TPU on the other hand, meanwhile also can reduce thermoplastic polyurethane cost, the work about this respect has caused the interest of people.That has reported has the blend alloys such as TPU/PC, POM/TPU, TPU/PP, TPU/PVC, PA/TPU, PS/TPU.
There is the various problems such as technological method is few, technology is immature, equipment requirements is special in the existing method preparing polymer alloy at present, and all have larger limitation, is all difficult to the universality method as preparing polymer alloy.As the mixing method of high speed high shear strength wherein, not only require to extrude the rotating speed that mixing facilities tool has hundreds to 1,000 hundreds of turns, and be only applicable to the extremely good polymer alloy system of consistency; There is harsh requirement the aspects such as reactive extrursion method not only controls the temperature of mixing facilities, pressure-controlling, sealing property, and must have stronger reactive behavior in polymer alloy system between material; It is after first being pulverized under lower temperature condition in special solid phase pulverizing unit by polymer alloy system that solid phase pulverizes rule, under the condition controlling mixing intensity, in mixing unit, make it to realize a kind of polymkeric substance be again dispersed in method in another polymkeric substance with nanoscale, this method not only needs to adopt special equipment and control condition, and the stable appearance of the alloy formed is also very poor.
In the bibliographical information delivered, researchist's main attention concentrates on certain macromolecular material blended for TPU, improves some performance of macromolecular material thus.But simple mixing can not reach superposition and the enhancing of storeroom performance, only has other blended both performance that just can make of molecular level to superpose, strengthen, occurs beyond thought effect.How obtaining between TPU and polymer blend and combine with other form of molecular level, is the difficulty that this patent is puted forth effort to solve.
summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, a kind of low cost is provided, there is the preparation method of the thermo plastic polyurethane alastic body alloy of high-modulus, high strength, snappiness and good workability.
Thinking of the present invention proposes a kind of method that polycondensation and radical polymerization are prepared polyurethane alloys simultaneously, thus, the various problem such as method and technology limitation large special to equipment requirements that exist in solution general polymerization thing reasonable offer.
Formula composition (weight part) of the present invention is:
| Unsaturated monomer | 10 ~ 100 parts |
| Initiator | 0.05 ~ 5 part |
| Polyvalent alcohol | 100 parts |
| Catalyzer | 0.1 ~ 0.5 part |
| Vulcabond | 40 ~ 50 parts |
| Small molecules glycol chain extender | 8 ~ 10 parts |
| Solvent | 250 ~ 2500 parts |
Preparation process of the present invention is:
(1) radical polymerization initiator of 0.05 ~ 5 part (weight part) is dissolved in the unsaturated monomer of 100 parts for subsequent use.
(2) polyvalent alcohol of 100 parts and 0.1 ~ 0.5 part of catalyzer are mixed for subsequent use in 70 DEG C.
(3) unsaturated monomer being dissolved with radical polymerization initiator of 10 ~ 100 parts and 100 parts are dissolved with polyvalent alcohol prepolymerization 0.5 ~ 2 h at 60 ~ 80 DEG C of catalyzer, add stirring solvent evenly after, add isocyanic ester and the chainextender of metering, at 80 ~ 100 DEG C, continue reaction 1 ~ 10 h, obtain polyurethane alloys solution.
(4) polyurethane alloys solution is dropped in water and make polyurethane alloys become block to separate out, to be broken into after pellet dry 3 ~ 8 h at 130 DEG C, to obtain polyurethane alloys pellet.
Described polyurethane alloys is reach other mixture of molecular level between the polymkeric substance that forms of main component by vulcabond, polyvalent alcohol and small molecules dibasic alcohol, unsaturated monomer and initiator.
Described unsaturated monomer, comprise vinylchlorid, vinylbenzene, vinyl acetate between to for plastic, vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxy ethyl phosphoric acid ester, isobornyl acrylate, vinylformic acid tetrahydrofuran (THF) methyl esters, methacrylic acid, methyl methacrylate, first class ethyl propenoate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid is ester, Isooctyl acrylate monomer, lauryl methacrylate(LMA), isobornyl methacrylate, one or more compositions in cyclohexyl methacrylate.
Initiator of the present invention is various azo-initiators, comprises Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), azo isobutyl cyano group methane amide (CANB), azo dicyclohexyl formonitrile HCN (ACCN), azo-bis-iso-dimethyl (AIBME); Or the initiator of various organo-peroxide class, the principal item comprising organo-peroxide has hydroperoxide (ROOH), dialkyl peroxide (ROOR), diacyl peroxide (RCOOOOCR), peroxy esters (RCOOOR), peroxycarbonates (ROCOOOOCOR) and ketone peroxide [R
2c (OOH)
2] in one or more composition.。
Vulcabond of the present invention can select aromatic diisocyanate or aliphatic diisocyanate, comprise one or more compositions in 4,4'-diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate.。
Catalyzer described in the present invention can select stannous octoate, dibutyl tin laurate etc., and wherein dibutyl tin laurate speed is fast, controls not with great difficulty gel.
The optional spent glycol of small molecules glycol chain extender of the present invention, BDO or 1,3-PD.
Solvent of the present invention can select purified petroleum benzin, N-BUTYL ACETATE, vinyl acetic monomer, dimethylbenzene, pimelinketone, acetone, N-Methyl pyrrolidone (NMP) and N, N-dimethyl amide (DMF).The solvent selected needs to consider solvency power, evaporation rate, can not select especially and its alcohol reacted of NCO base, ether alcohol class equal solvent, and can not contain the impurity such as water, alcohol in solvent, can not contain alkaloids.
Compared with prior art, the present invention has following outstanding feature and significant advantage: the present invention has that preparation is simple, other is blended to reach molecular level between polymkeric substance, solve the problem of urethane and polyolefine mixing poor compatibility, the polyurethane alloys of invention has good toughness, strength and modulus all comparatively advantages of higher.
embodiment:
Following examples only for explaining the present invention, do not form limiting the scope of the present invention, and wherein in embodiment, unsaturated monomer selects one of them butyl acrylate to be example.
embodiment 1
First, taking 2 g initiator A IBN is dissolved in 100 g Butyl Acrylate Monomers for subsequent use; Secondly, take the sub-tin of 0.25 g octoate catalyst and add and fill in 100 g polyester polyols (poly-hexanodioic acid butyl ester glycol dried in advance, hydroxyl value 106 mg KOH/g, acid number 2 mg KOH/g) beaker, mixing for standby use at 70 DEG C; Then, in the dry reaction still being connected with thermometer, agitator, prolong and gas inlet and outlet, the polyester polyol that the unsaturated monomer and 100 40.8 g being dissolved with radical initiator is dissolved with catalyzer is uniformly mixed, and temperature controls prepolymerization 0.5 ~ 2 h at 75 DEG C; Add in reactor again 500 mL stirring solvent evenly after, add 47.9 g isocyanic ester ('-diphenylmethane diisocyanates dried in advance, MDI) and 8.02 g glycol chain extenders, temperature controls at 95 DEG C, continue reaction 9 h, obtains polyurethane alloys solution; Finally polyurethane alloys solution is dropped in water and make polyurethane alloys become block to separate out, to be broken into after pellet dry 6 h at 130 DEG C, to obtain thermo plastic polyurethane alastic body alloy micelle.
Embodiment 2
First, taking 2 g initiator A IBN is dissolved in 100 g Butyl Acrylate Monomers for subsequent use; Secondly, take the sub-tin of 0.25 g octoate catalyst and add and fill in 100 g polyester polyols (poly-hexanodioic acid butyl ester glycol dried in advance, hydroxyl value 106 mg KOH/g, acid number 2 mg KOH/g) flask, mixing for standby use at 70 DEG C; Then, in the dry reaction still being connected with thermometer, agitator, prolong and gas inlet and outlet, the polyester polyol that the unsaturated monomer and 100 30.6 g being dissolved with radical initiator is dissolved with catalyzer is uniformly mixed, and temperature controls prepolymerization 0.5 ~ 2 h at 75 DEG C; Add in reactor again 500 mL stirring solvent evenly after, add 47.8 g isocyanic ester ('-diphenylmethane diisocyanates dried in advance, MDI) and 8.0 g glycol chain extenders, temperature controls at 95 DEG C, continue reaction 9 h, obtains polyurethane alloys solution; Finally polyurethane alloys solution is dropped in water and make polyurethane alloys become block to separate out, to be broken into after pellet dry 6 h at 130 DEG C, to obtain thermo plastic polyurethane alastic body alloy micelle.
Embodiment 3
First, taking 2 g initiator A IBN is dissolved in 100 g Butyl Acrylate Monomers for subsequent use; Secondly, take the sub-tin of 0.25 g octoate catalyst and add and fill in 100 g polyester polyols (poly-hexanodioic acid butyl ester glycol dried in advance, hydroxyl value 106 mg KOH/g, acid number 2 mg KOH/g) flask, mixing for standby use at 70 DEG C; Then, in the dry reaction still being connected with thermometer, agitator, prolong and gas inlet and outlet, the polyester polyol that the unsaturated monomer and 100 20.4 g being dissolved with radical initiator is dissolved with catalyzer is uniformly mixed, and temperature controls prepolymerization 0.5 ~ 2 h at 75 DEG C; Add in reactor again 500 mL stirring solvent evenly after, add 47.8 g isocyanic ester ('-diphenylmethane diisocyanates dried in advance, MDI) and 8.0 g glycol chain extenders, temperature controls at 95 DEG C, continue reaction 9 h, obtains polyurethane alloys solution; Finally polyurethane alloys solution is dropped in water and make polyurethane alloys become block to separate out, to be broken into after pellet dry 6 h at 130 DEG C, to obtain thermo plastic polyurethane alastic body alloy micelle.
Claims (8)
1. solution method prepares a method for polyurethane alloys, it is characterized in that:
1.1 its formulas composition (weight part) are:
1.2 its preparation process are:
(1) radical polymerization initiator of 0.05 ~ 5 part (weight part) is dissolved in the unsaturated monomer of 100 parts for subsequent use;
(2) polyvalent alcohol of 100 parts and 0.1 ~ 0.5 part of catalyzer are mixed for subsequent use in 70 DEG C;
(3) unsaturated monomer being dissolved with radical polymerization initiator of 10 ~ 100 parts and 100 parts are dissolved with polyvalent alcohol prepolymerization 0.5 ~ 2 h at 60 ~ 80 DEG C of catalyzer, add stirring solvent evenly after, add isocyanic ester and the chainextender of metering, at 80 ~ 100 DEG C, continue reaction 1 ~ 10 h, obtain polyurethane alloys solution;
(4) polyurethane alloys solution is dropped in water and make polyurethane alloys become block to separate out, to be broken into after pellet dry 3 ~ 8 h at 130 DEG C, to obtain polyurethane alloys pellet.
2. a kind of solution method according to claim 1 prepares the method for polyurethane alloys, and it is characterized in that described polyurethane alloys is is reach other mixture of molecular level between the polymkeric substance that forms of main component by vulcabond, polyvalent alcohol and small molecules dibasic alcohol, unsaturated monomer and initiator.
3. a kind of solution method according to claim 1 prepares the method for polyurethane alloys, it is characterized in that described unsaturated monomer, by vinylchlorid, vinylbenzene, vinyl acetate between to for plastic, vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, perfluoroalkyl acrylate, hydroxy ethyl phosphoric acid ester, isobornyl acrylate, vinylformic acid tetrahydrofuran (THF) methyl esters, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid is ester, Isooctyl acrylate monomer, lauryl methacrylate(LMA), isobornyl methacrylate, one or more compositions in cyclohexyl methacrylate.
4. a kind of solution method according to claim 1 prepares the method for polyurethane alloys, it is characterized in that described initiator is various azo-initiators, by Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), azo isobutyl cyano group methane amide (CANB), azo dicyclohexyl formonitrile HCN (ACCN), azo-bis-iso-dimethyl (AIBME); Or the initiator of various organo-peroxide class, the principal item comprising organo-peroxide has hydroperoxide (ROOH), dialkyl peroxide (ROOR), diacyl peroxide (RCOOOOCR), peroxy esters (RCOOOR), peroxycarbonates (ROCOOOOCOR) and ketone peroxide [R
2c (OOH)
2] in one or more composition.
5. a kind of solution method according to claim 1 prepares the method for polyurethane alloys, it is characterized in that described vulcabond is that aromatic diisocyanate or aliphatic diisocyanate are made up of one or more in 4,4'-diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate.
6. a kind of solution method according to claim 1 prepares the method for polyurethane alloys, it is characterized in that the described optional spent glycol of small molecules glycol chain extender, BDO or 1,3-PD.
7. a kind of solution method according to claim 1 prepares the method for polyurethane alloys, it is characterized in that described solvent can select purified petroleum benzin, N-BUTYL ACETATE, vinyl acetic monomer, dimethylbenzene, pimelinketone, acetone, N-Methyl pyrrolidone (NMP) and N, N-dimethyl amide (DMF); The solvent selected needs to consider solvency power, evaporation rate, can not select especially and its alcohol reacted of NCO base, ether alcohol class equal solvent, and can not contain the impurity such as water, alcohol in solvent, can not contain alkaloids.
8. a kind of solution method according to claim 1 prepares the method for polyurethane alloys, it is characterized in that described catalyzer can select stannous octoate, dibutyl tin laurate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510426214.XA CN105001623A (en) | 2015-07-20 | 2015-07-20 | Solution method-based method for preparing polyurethane alloy |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219340A (en) * | 2018-01-03 | 2018-06-29 | 温州市登达化工有限公司 | A kind of soft cross-linked polyurethane materials and preparation method thereof |
| CN115894848A (en) * | 2022-11-25 | 2023-04-04 | 上海抚佳精细化工有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060148985A1 (en) * | 2003-07-04 | 2006-07-06 | Nanon A/S | Method of producing an interpenetrating polymer network (ipn), the ipn and use thereof |
| CN101108889A (en) * | 2007-06-05 | 2008-01-23 | 北京化工大学 | A polyurethane/vinyl polymer IPN two-component damping material |
-
2015
- 2015-07-20 CN CN201510426214.XA patent/CN105001623A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060148985A1 (en) * | 2003-07-04 | 2006-07-06 | Nanon A/S | Method of producing an interpenetrating polymer network (ipn), the ipn and use thereof |
| CN101108889A (en) * | 2007-06-05 | 2008-01-23 | 北京化工大学 | A polyurethane/vinyl polymer IPN two-component damping material |
Non-Patent Citations (1)
| Title |
|---|
| 代正伟等: ""PU/PNIPAM semi-IPN 微孔膜温度响应性研究"", 《高分子学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219340A (en) * | 2018-01-03 | 2018-06-29 | 温州市登达化工有限公司 | A kind of soft cross-linked polyurethane materials and preparation method thereof |
| CN115894848A (en) * | 2022-11-25 | 2023-04-04 | 上海抚佳精细化工有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
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Application publication date: 20151028 |