CN1597737A - Polyether thiosulphone copolymer and its preparation method - Google Patents
Polyether thiosulphone copolymer and its preparation method Download PDFInfo
- Publication number
- CN1597737A CN1597737A CN 200410040365 CN200410040365A CN1597737A CN 1597737 A CN1597737 A CN 1597737A CN 200410040365 CN200410040365 CN 200410040365 CN 200410040365 A CN200410040365 A CN 200410040365A CN 1597737 A CN1597737 A CN 1597737A
- Authority
- CN
- China
- Prior art keywords
- sulfone
- parts
- copolymer
- grams
- sodium
- 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
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
A polyarylthioether sulfone is prepared through proportionally mixing solvent, assistant, catalyst, azeotropic agent and water, stirring, adding Na2S.xH2O and dihalobiphenyl sulfone, dewatering reacting under protection of N2 to obtain polyaryl thioether sulfone oligomerm adding dihalodiphenyl sulfone and aromatic halocompound, reacting to obtain low-molecular copolymer, and reacting to obtain high-molecular copolymer.
Description
One, technical field
The present invention relates to a kind of poly arylidene thio-ester sulfone copolymer and preparation method thereof, belong to the synthetic field of high molecular polymer.
Two, background technology
Poly arylidene thio-ester is the special engineering plastics of a class excellent property, has good mechanical performance and resistance toheat, dimensional stability, flame retardant resistance etc.Polyphenylene sulfide, polyphenylene sulfide ketone of crystal type etc. are arranged in them, unformed PPSS etc. is also arranged, the present invention has in preparation on the basis of polyphenylene sulfide sulphone resin of excellent mechanical property and high Tg, introduce copolymerization the 3rd monomer, further improve the performance of PPSS, particularly the advantages of itself and crystal polymer thing is got up, obtained existing good heat-resisting, chemical resistance, be easy to the modified polyphenyl thioether sulphone resin of processing again.This polymkeric substance can be used as high performance polymer matrix material and special engineering plastics resin base, can prepare the electric insulating film and the separatory membrane of heatproof, resistance to chemical attack again, is with a wide range of applications.
J.Polym.Sci.part A, Vol.32 (1994) and U.S. Pat patent 4016145 have reported and have used Sodium sulfhydrate, 4,4-dichloro diphenyl sulfone, 4, the 4-difluoro benzophenone under high pressure is that catalyzer has synthesized PPSS/ketone copolymers with the carboxylate salt, but this method complicated operation, the energy consumption height; The synthetic molecular weight product is low, so product mechanical property and electrical property are undesirable, have limited use range.
Three, summary of the invention
The objective of the invention is provides a kind of poly arylidene thio-ester sulfone copolymer and preparation method thereof at the deficiencies in the prior art, be characterized in adopting efficient composite catalyst, promotor, auxiliary agent, azeotropy dehydrant etc. are by the poly arylidene thio-ester sulfone copolymer of polymeric method synthetic macromolecule amount, excellent combination property progressively.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Poly arylidene thio-ester sulfone copolymer starting raw material recipe ingredient is:
Na
2SxH
2O Na
260% 100 parts of S content ≈
Perhaps NaHS is 43 parts
110～221 parts of dihalo diphenyl sulfones
3.3～318 parts of halogenated aromatic compounds
2～15 parts of catalyzer
Auxiliary agent 1～20
420～1000 parts of solvents
0～40 part of entrainer
0～25 part of deionized water
Wherein dihalo diphenyl sulfone is any in dichloro diphenyl sulfone, dibromo sulfobenzide or the difluorodiphenyl sulfone, halogenated aromatic compound is the dihalo benzophenone, in p-phthaloyl chloride, dihalo phenyl ether, dihalo diphenyl sulfide, the pentafluorophenyl group sulfone any.
Catalyzer be tertiary sodium phosphate, sodium-acetate, Lithium Acetate, hydroxy acid sodium, lithium chloride, epsilon-amino caproic acid, hexanolactam, p-methyl benzenesulfonic acid sodium and or Sodium Benzoate at least a.
Auxiliary agent is at least a in Paraformaldehyde 96, phenyl aldehyde, sodium formiate, sodium borohydride or the sodium hydroxide.
Solvent is at least a in N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), HMPA, dimethyl formamide, N-cyclohexyl pyrrolidone, N,N-DIMETHYLACETAMIDE and N-methyl caprolactam or the sulfobenzide.
Azeotropy dehydrant is toluene or dimethylbenzene.
The preparation method of poly arylidene thio-ester sulfone copolymer
1, Na
2SxH
2The preparation of O dehydration and polyaryl thioether sulfone oligopolymer
With 420～1000 parts of solvents, 1～20 part of auxiliary agent and 2～15 parts of addings of catalyzer have N
2Gas is come in and gone out and is managed, agitator, and in the reactor of thermometer and water trap, the back that stirs adds Na
2SxH
2O (Na
2S content ≈ 60%) 100 parts or 43 parts of NaHS, 25～45 parts of dihalo diphenyl sulfones under nitrogen protection, in dehydration reaction between 100～160 ℃ of temperature 0.3～4 hour, form the polyaryl thioether sulfone oligopolymer simultaneously.
2, the preparation of copolymerized oligomer
To add 75～186 parts of dihalo diphenyl sulfones in the above-mentioned reactant, 3.3～318 parts of halogenated aromatic compounds in 120～140 ℃ of reactions of temperature 10～60 minutes, make low-molecular-weight co-polymer.
3, the preparation of high-molecular weight polymer
Above-mentioned oligopolymer is continued reaction 0.5～6 hour for 160～204 ℃ in temperature, obtain high molecular poly arylidene thio-ester sulfone copolymer product.
4, purifying products
The said products is poured in the precipitation agent water while hot, separated out this polymkeric substance, cooling is after pulverize, wash the dry poly arylidene thio-ester sulfone copolymer that obtains following structure:
Wherein, n=1～150, m=1～100, Ar is
R
1～8For-SO
3H ,-H ,-COO, F ,-CN ,-CH
3,-CH
2ClN (CH
3)
3, Y is-SO
2-,-CO-,-O-,-S-,
By regulating monomer sulfone and the 3rd monomeric proportioning, regulate and control temperature of reaction and reaction times and feed way etc., can prepare the high molecular polyaryl thioether sulfone co-polymer of different the 3rd monomer content, different crystallization degree and different viscosity.This copolymer solution intrinsic viscosity η=0.39～0.86dl/g, second-order transition temperature Tg is 144～238 ℃, heat-drawn wire T 〉=180 ℃, heat decomposition temperature T
d〉=460 ℃.
The present invention has following advantage:
1, can be under normal pressure can depress the synthetic multiple high molecular weight polyphenylene sulfide sulfone copolymer that features is arranged adding again;
2, adopt efficient composite catalyst, experimental repeatability is strong, product stability good, the yield height;
3, reaction can both obtain better products in multiple solvent;
4, progressively polymerization improves product yield and performance and has played keying action the molecular weight and the molecular weight distribution of control resin.
Four, embodiment
The following examples are to specifically describe of the present invention; be necessary to be pointed out that at this present embodiment only is used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can do some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
With N-Methyl pyrrolidone 528 grams, sodium hydroxide 5 grams, sodium formiate 10 restrain and lithium chloride 5.5 grams, deionized water 10 grams, and toluene 30 grams add and have nitrogen discrepancy pipe, and agitator after stirring in the reactor of thermometer and water trap, adds Na again
2SxH
2O (Containing Sulfur sodium ≈ 60%) 100 grams; dichloro-sulfobenzide 46.2 grams; under nitrogen protection, heat temperature raising to 190 ℃ divides water outlet 70.0 grams and toluene 30 to restrain; be cooled to 120 ℃ then; add 4,4-two fluoro dimethylbenzene ketone 59.0 grams, dichloro-sulfobenzide 97.4 grams; be warmed up to 200 ℃ through 0.5～1 hour, then 190～220 ℃ of reactions of temperature 0.5～12 hour.Product poured in the water precipitates, after the filtration, use hot wash, again with product in 80 ℃ of vacuum-dryings of temperature, obtain polyaryl thioether sulfone/ketone copolymers, productive rate is 96%.
Embodiment 2
With sulfobenzide 564 gram, sodium hydroxide 6 grams, sodium formiate 6 grams and sodium-acetate 10 grams, toluene 30 grams, deionized water 6 grams in the identical equipment of adding embodiment 1, after stirring, add Na again
2SxH
2O 100 grams, dichloro-sulfobenzide 22.1 grams are under nitrogen protection; be warming up to 200 ℃, divide water outlet 76 grams, be cooled to 120 ℃ then; add dichloro-sulfobenzide 88.2 grams, 4,4-two fluoro dimethylbenzene ketone 89.7 grams; through 0.5～1 hour, be warming up to 200 ℃, after 200～210 ℃ of temperature are reacted 0.5～12 hour; pour in the water product, after filtering, use hot wash, again with product in 80 ℃ of vacuum-dryings of temperature; obtain polyaryl thioether sulfone/ketone copolymers, productive rate is 94%.
Embodiment 3
With N-cyclohexyl pyrrolidone 538 grams; sodium hydroxide 4 grams; Paraformaldehyde 96 6 grams and Sodium Benzoate 6 grams; deionized water 6 gram adds in the identical equipment of embodiment 1, after stirring; add NaHS 43 grams again; dichloro-sulfobenzide 26.7 grams under nitrogen protection, are warming up to 180 ℃; divide water outlet 74 grams; be cooled to 110 ℃ and add dichloro-sulfobenzide 105.6 grams then, 4,4-two fluoro dimethylbenzene ketone 67.2 grams; through 0.5～1 hour; be warming up to 200 ℃, after 0.5～12 hour, product poured in the water in 200～280 ℃ of reactions of temperature; after filtering; use hot wash; again with product in 80 ℃ of vacuum-dryings of temperature, obtain polyaryl thioether sulfone/ketone copolymers, productive rate is 95%.
Embodiment 4
With N,N-DIMETHYLACETAMIDE 530 grams; sodium hydroxide 3 gram, phenyl aldehyde 5 grams and oxyacetic acid are received 5 grams, in the identical equipment of adding embodiment 1; after stirring; add NaHS 43 grams again, dichloro-sulfobenzide 35.9 grams are warming up to 180 ℃ under nitrogen protection; divide water outlet 73 grams; be cooled to 120 ℃ and add dichloro-sulfobenzide 141.0 grams then, 4,4-dibromodiphenyl ether 38.2 grams; through 0.5～1 hour; be warming up to 200 ℃, after 0.5～12 hour, product poured in the water in 200～280 ℃ of reactions of temperature; after filtering; use hot wash; again with product in 80 ℃ of vacuum-dryings of temperature, obtain the poly arylidene thio-ester sulfone copolymer, productive rate is 95%.
Embodiment 5
Dimethyl sulfoxide (DMSO) 540 gram, sodium hydroxide 2 grams, formic acid are received 6 grams and Sodium Benzoate 6 grams, and deionized water 6 grams in the identical equipment of adding embodiment 1, after stirring, add Na again
2SxH
2O 100 grams, dichloro-sulfobenzide 35.9 grams are warming up to 180 ℃ under nitrogen protection; divide water outlet 72 grams, be cooled to 110 ℃ and add dichloro-sulfobenzide 141.0 grams, 4 then; 4-dibromodiphenyl ether 38.2 grams through 0.5～1 hour, are warming up to 200 ℃; after 200～280 ℃ of temperature are reacted 0.5～12 hour; pour in the water product, after filtering, use hot wash, again with product in 80 ℃ of vacuum-dryings of temperature; obtain the poly arylidene thio-ester sulfone copolymer, productive rate is 95%.
Embodiment 6
HMPA 538.5 gram, sodium hydroxide 4 grams, formic acid are received 6 grams and paratoluenesulfonic acid sodium salt 6 grams, and deionized water 6 grams in the identical equipment of adding embodiment 1, after stirring, add Na again
2SxH
2O 100 grams, dichloro-sulfobenzide 35.9 grams are warming up to 180 ℃ under nitrogen protection; divide water outlet 78 grams, be cooled to 110 ℃ and add dichloro-sulfobenzide 74.4 grams, 4 then; 4-dibromodiphenyl ether 95.4 grams through 0.5～1 hour, are warming up to 200 ℃; after 200～280 ℃ of temperature are reacted 0.5～12 hour; pour in the water product, after filtering, use hot wash, again with product in 80 ℃ of vacuum-dryings of temperature; obtain the poly arylidene thio-ester sulfone copolymer, productive rate is 94%.
Claims (6)
1, poly arylidene thio-ester sulfone copolymer is characterized in that this multipolymer starting raw material recipe ingredient is by weight:
Na
2SxH
2O Na
260% 100 parts of S content ≈
Perhaps NaHS is 43 parts
110～221 parts of dihalo diphenyl sulfones
3.3～318 parts of halogenated aromatic compounds
2～15 parts of catalyzer
1～20 part of auxiliary agent
420～1000 parts of solvents
0～40 part of entrainer
0～25 part of deionized water
Wherein dihalo diphenyl sulfone is dichloro-sulfobenzide, two bromo sulfobenzides or difluorodiphenyl sulfone, halogenated aromatic compound is the dihalo benzophenone, in p-phthaloyl chloride, dihalo phenyl ether, dihalo diphenyl sulfide, the pentafluorophenyl group sulfone any, this copolymer solution intrinsic viscosity η=0.39～0.86dl/g, second-order transition temperature Tg is 144～238 ℃, heat-drawn wire T 〉=180 ℃, heat decomposition temperature T
d〉=460 ℃.
2,, it is characterized in that catalyzer is at least a in tertiary sodium phosphate, sodium-acetate, Lithium Acetate, hydroxy acid sodium, lithium chloride, epsilon-amino caproic acid, hexanolactam, p-methyl benzenesulfonic acid sodium or the Sodium Benzoate according to the described poly arylidene thio-ester sulfone copolymer of claim 1.
3,, it is characterized in that auxiliary agent is at least a in Paraformaldehyde 96, phenyl aldehyde, sodium formiate, sodium borohydride or the sodium hydroxide according to the described poly arylidene thio-ester sulfone copolymer of claim 1.
4,, it is characterized in that solvent is at least a in N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), HMPA, dimethyl formamide, N-cyclohexyl pyrrolidone, N,N-DIMETHYLACETAMIDE and N-methyl caprolactam or the sulfobenzide according to the described poly arylidene thio-ester sulfone copolymer of claim 1.
5,, it is characterized in that entrainer is toluene or dimethylbenzene according to the described poly arylidene thio-ester sulfone copolymer of claim 1.
6, according to the preparation method of the described poly arylidene thio-ester sulfone copolymer of claim 1～5, it is characterized in that:
(1) Na
2SxH
2The preparation of O dehydration and polyaryl thioether sulfone oligopolymer
With solvent 420～1000 weight parts, auxiliary agent 1～20 weight part, catalyzer 2～15 weight parts, entrainer 0～40 weight part, deionized water 0～25 weight part adds and has nitrogen discrepancy pipe, agitator, in the reactor of thermometer and water trap, the back that stirs adds Na
2SxH
2O (Na
2S content ≈ 60%) 100 weight parts or NaHS43 weight part, dihalo diphenyl sulfone 25～45 weight parts under nitrogen protection, in dehydration reaction between 100～160 ℃ of temperature 0.3～4 hour, form the polyaryl thioether sulfone oligopolymer simultaneously;
(2) preparation of copolymerized oligomer
To add dihalo diphenyl sulfone 75～186 weight parts in the above-mentioned reactant, halogenated aromatic compound 3.3～318 weight parts in 120～140 ℃ of reactions of temperature 10～60 minutes, make low-molecular-weight co-polymer;
(3) preparation of high-molecular weight polymer
Above-mentioned oligopolymer is continued reaction 0.5～6 hour for 160～204 ℃ in temperature, obtain high molecular poly arylidene thio-ester sulfone copolymer product;
(4) purifying products
The said products is poured in the precipitation agent water while hot, is separated out this polymkeric substance, cooling after pulverize, washing is dry, obtains the poly arylidene thio-ester sulfone copolymer of following structure:
Wherein, n=1～150, m=1～100, Ar is
R
1～8For-SO
3H ,-H ,-COO, F ,-CN ,-CH
3,-CH
2ClN (CH
3)
3, Y is-SO
2-,-CO-,-O-,-S-,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410040365 CN1597737A (en) | 2004-08-04 | 2004-08-04 | Polyether thiosulphone copolymer and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410040365 CN1597737A (en) | 2004-08-04 | 2004-08-04 | Polyether thiosulphone copolymer and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1597737A true CN1597737A (en) | 2005-03-23 |
Family
ID=34664630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410040365 Pending CN1597737A (en) | 2004-08-04 | 2004-08-04 | Polyether thiosulphone copolymer and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1597737A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101668814B (en) * | 2007-04-23 | 2012-08-08 | 索维高级聚合物股份有限公司 | Thermoplastic polymer mixtures, and applications thereof |
| CN103087523A (en) * | 2012-12-26 | 2013-05-08 | 四川大学 | Extrusion-grade polyarylene sulfide bar and preparation method thereof |
| CN104292463A (en) * | 2014-09-19 | 2015-01-21 | 中山市鸿程科研技术服务有限公司 | Polyarylene sulfide sulfone and preparation method thereof |
| CN105622939A (en) * | 2016-03-21 | 2016-06-01 | 成都大诺工程技术咨询有限公司 | Preparation method for polyarylenesulfidesulfone |
| CN105778095A (en) * | 2016-03-21 | 2016-07-20 | 成都大诺工程技术咨询有限公司 | Low-oxygen polyarylene sulfide sulfone synthetic technology |
| CN106243356A (en) * | 2016-08-30 | 2016-12-21 | 四川金和成科技有限公司 | A kind of manufacture method of high molecular weight polyphenylene sulfide sulfone ketone |
| CN106750302A (en) * | 2017-01-13 | 2017-05-31 | 四川中科兴业高新材料有限公司 | A kind of preparation method of heat resistance, corrosion resistant HMW poly arylidene thio-ester sulfone |
| CN107501555A (en) * | 2017-07-27 | 2017-12-22 | 四川中科兴业高新材料有限公司 | A kind of method of quickly synthesis in low temperature polyaryl thioether sulfone |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
-
2004
- 2004-08-04 CN CN 200410040365 patent/CN1597737A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101668814B (en) * | 2007-04-23 | 2012-08-08 | 索维高级聚合物股份有限公司 | Thermoplastic polymer mixtures, and applications thereof |
| CN103087523A (en) * | 2012-12-26 | 2013-05-08 | 四川大学 | Extrusion-grade polyarylene sulfide bar and preparation method thereof |
| CN103087523B (en) * | 2012-12-26 | 2014-08-27 | 四川大学 | Extrusion-grade polyarylene sulfide bar and preparation method thereof |
| CN104292463A (en) * | 2014-09-19 | 2015-01-21 | 中山市鸿程科研技术服务有限公司 | Polyarylene sulfide sulfone and preparation method thereof |
| CN105622939A (en) * | 2016-03-21 | 2016-06-01 | 成都大诺工程技术咨询有限公司 | Preparation method for polyarylenesulfidesulfone |
| CN105778095A (en) * | 2016-03-21 | 2016-07-20 | 成都大诺工程技术咨询有限公司 | Low-oxygen polyarylene sulfide sulfone synthetic technology |
| CN106243356A (en) * | 2016-08-30 | 2016-12-21 | 四川金和成科技有限公司 | A kind of manufacture method of high molecular weight polyphenylene sulfide sulfone ketone |
| CN106750302A (en) * | 2017-01-13 | 2017-05-31 | 四川中科兴业高新材料有限公司 | A kind of preparation method of heat resistance, corrosion resistant HMW poly arylidene thio-ester sulfone |
| CN106750302B (en) * | 2017-01-13 | 2019-01-08 | 四川中科兴业高新材料有限公司 | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone |
| CN107501555A (en) * | 2017-07-27 | 2017-12-22 | 四川中科兴业高新材料有限公司 | A kind of method of quickly synthesis in low temperature polyaryl thioether sulfone |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101702936B1 (en) | High Temperature melt processable semi-crystalline poly (aryl ether ketone) containing a (4-hydroxyphenyl)phthalazin-1(2H)-one comonomer unit | |
| KR101466241B1 (en) | Preparation method of terpolymer containing segment i and segment ii | |
| CN101759546B (en) | Phenylacetylene-capped polyether-ether-ketone oligomer and preparation method thereof | |
| CA2671870C (en) | High temperature stable polyelectrolytes having backbone aromatic groups | |
| JP2007530763A (en) | Improved process for the preparation of block copolymers and block copolymers prepared therefrom | |
| AU2005227754A1 (en) | An improved process of preparation of block copolymers and the block copolymers prepared therefrom | |
| CN1058729C (en) | Polyaryl ether nitrile and producing process thereof | |
| CN1597737A (en) | Polyether thiosulphone copolymer and its preparation method | |
| CN1195002C (en) | Polyaryl thioether sulfone and its preparation method | |
| Wang et al. | Synthesis and characterization of poly (arylene ether ketone)(co) polymers containing sulfonate groups | |
| CN111403785A (en) | Sulfonated polyaryletherketone sulfone composite membrane and preparation method thereof | |
| JP5585119B2 (en) | Process for producing polyarylene sulfide | |
| CN102952269B (en) | Polyarylenesulfidesulfone/polyethersulfone copolymer and preparation method thereof | |
| JPH09309945A (en) | Polyphenylene copolymer | |
| CN110358087B (en) | Di-sulfonated polyarylthioether phosphine oxide containing phthalazinone and preparation method and application thereof | |
| CN116813897A (en) | PET nucleating agent and preparation method and application thereof | |
| CN1291973C (en) | 1,3-di(3-sodium sulfonate group-4-fluoro-benzoyl) benzene and polymers and their synthesis method | |
| CN1091116C (en) | Polyaryl ether-nitrile-sulfone containing phenolphthalein structure and its preparing process | |
| CN1332187A (en) | Polyester sulphone with lateral carboxylate group and its prepn | |
| CN111410746B (en) | Hyperbranched polysulfone with controllable branching degree and preparation method thereof | |
| JP5070071B2 (en) | Polyphenylene copolymer | |
| CN111548495A (en) | Polyarylene sulfide sulfone containing phthalazinone structure and preparation method thereof | |
| CN1702099A (en) | Sulphonated poly(aryl ether ketone) block polybutadiene copolymer and process for preparing same | |
| CN113501954B (en) | Sulfonated aromatic phosphine oxide polymer containing hydroquinone and preparation method and application thereof | |
| TWI272280B (en) | Process for continuous production of branched polyarylene sulfides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |