CN101831842B - Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof - Google Patents
Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof Download PDFInfo
- Publication number
- CN101831842B CN101831842B CN201010187129XA CN201010187129A CN101831842B CN 101831842 B CN101831842 B CN 101831842B CN 201010187129X A CN201010187129X A CN 201010187129XA CN 201010187129 A CN201010187129 A CN 201010187129A CN 101831842 B CN101831842 B CN 101831842B
- Authority
- CN
- China
- Prior art keywords
- add
- reinforcing agent
- silicon
- fluorine
- parts
- 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.)
- Active
Links
- 239000012744 reinforcing agent Substances 0.000 title claims abstract description 63
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 56
- 239000011737 fluorine Substances 0.000 title claims abstract description 56
- 238000004026 adhesive bonding Methods 0.000 title claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 33
- 239000010703 silicon Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000013543 active substance Substances 0.000 claims abstract description 47
- 125000002091 cationic group Chemical group 0.000 claims abstract description 47
- 238000005303 weighing Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 8
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 34
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 24
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- JXKUQNXYFYGNLY-UHFFFAOYSA-N hexadecyl(propyl)azanium chloride Chemical compound [Cl-].C(CCCCCCCCCCCCCCC)[NH2+]CCC JXKUQNXYFYGNLY-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- -1 acrylic ester Chemical class 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract 1
- 235000019394 potassium persulphate Nutrition 0.000 description 9
- 239000003292 glue Substances 0.000 description 6
- 230000035800 maturation Effects 0.000 description 5
- 238000004513 sizing Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 235000004258 Cordia alliodora Nutrition 0.000 description 1
- 244000085692 Cordia alliodora Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a novel fluorine-containing and silicon-containing gluing reinforcing agent and a preparation method thereof. The reinforcing agent is prepared from the following effective raw materials in part by weight: 30 to 40 parts of styrene, 30 to 40 parts of acrylic ester, 4 to 15 parts of fluorine-containing monomer and 5 to 10 parts of silicon-containing monomer. The method for preparing the fluorine-containing and silicon-containing gluing reinforcing agent comprises the following steps of: (1) weighing the raw materials in part by weight and uniformly mixing the raw materials; (2) weighing 35 to 45 percent of the mixture obtained by the step (1) and adding 6 to 8 parts of initiator and 30 to 40 parts of cationic active agent into the mixture; (3) raising the reaction temperature to between 80 and 90 DEG C, adding 35 to 45 percent of the mixture obtained by the step (1) again to perform reaction for 30 to 60 minutes, adding the remaining part of the mixture obtained by the step (1), adding 1 to 3 parts of initiator and 15 to 25 parts of cationic active agent and controlling the temperature to be between 80 and 90 DEG C to perform reaction for 2 to 3 hours; and (4) lowering the temperature to between 55 and 50 DEG C, adding 3 to 5 parts of NaHSO3 and cooling to normal temperature to prepare the fluorine-containing and silicon-containing gluing reinforcing agent. Since a fluorine-containing and silicon-containing initiator is added in a co-polymerization reaction process, the dispersivity and water solubility of a finished product are improved.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of paper for surface sizing reinforcing agent specifically, also relate to the preparation method of this reinforcing agent.
Background technology
At present domestic to have with styrene, butyl acrylate be principal monomer, and fluorochemical monomer (methacrylic acid ten difluoro heptyl esters) as auxiliary material, carries out the technical study and the application of Cypres.But there is following shortcoming in this gluing reinforcing agent: (making a concrete analysis of the deficiency of this reinforcing agent in the application of paper, long and so on like you) said maturation period of back.Another kind is to adopt the silicon solution of different degree of hydrolysis and the surface sizing strengthening agent that polyvinyl alcohol water solution is re-dubbed; And the VTES modifying cinepazid emulsion is used in the paper covering with paint; Domestic existing report research does not let fluorine-containing silicon-containing monomer (methacrylic acid ten difluoro fat in heptan, VTES) participate in the research and the application of copolyreaction synthetic surface gluing reinforcing agent as assistant but all have simultaneously.Not enough below this siliceous gluing reinforcing agent exists: (making a concrete analysis of the deficiency of this reinforcing agent in the application of paper, long and so on) like you said maturation period of back.The defective that present in sum gluing reinforcing agent both domestic and external exists is: can not well solve the paper problem of getting damp, and the applying glue cost of paper is higher, when system's applying glue, is subject to the extraneous factor influence, the maturation period is long, and WATER RESISTANCE is relatively poor.
Summary of the invention
The object of the invention just is to overcome above-mentioned deficiency siliceous gluing reinforcing agent of a kind of novel fluorine and preparation method thereof is provided; Solved the paper that the influences the industry product quality for a long time problem of getting damp; Improve the paper product quality simultaneously; Shorten the curing time, make applying glue each item index relatively stable, keep the paper manufacturing systems cleaning.
The object of the invention can be realized through following measure:
The siliceous gluing reinforcing agent of a kind of novel fluorine is formed by effective feedstock production of following weight portion: styrene 30-40, acrylic acid ester 30-40, fluorochemical monomer 4-15, silicon-containing monomer 5-10.
The siliceous gluing reinforcing agent of above-mentioned novel fluorine is formed by the feedstock production of following weight portion: styrene 30-40, acrylic acid ester 30-40, fluorochemical monomer 4-15, silicon-containing monomer 5-10, initator 7-11 part, cationic active agent 45-65.
The siliceous gluing reinforcing agent of above-mentioned novel fluorine, described initator are KPS, (NH
4)
2S
2O
8, KM
nO
4In any, cationic active agent is any in methylacryoyloxyethyl trimethyl ammonium chloride or 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or the palmityl propyl ammonium chloride.
The siliceous gluing reinforcing agent of above-mentioned novel fluorine is formed by the feedstock production of following weight portion: styrene 35, acrylic acid ester 35, fluorochemical monomer 7, silicon-containing monomer 5.3.
The siliceous gluing reinforcing agent of above-mentioned novel fluorine; Said fluorochemical monomer is any in methacrylic acid ten difluoro fat in heptan, methacrylic acid hexafluoro fourth fat or the methacrylic acid trifluoro second fat, and silicon-containing monomer is any in VTES or VTES, vinyltrimethoxy silane, propyl trimethoxy silicane, the Y-propyl trimethoxy silicane.
The preparation method of the siliceous gluing reinforcing agent of a kind of novel fluorine may further comprise the steps: 1. take by weighing each raw material by weight, and each raw materials mix is even;
2. take by weighing the 1. 35%-45% of gained mixture of step, add initator 6-8 part, cationic active agent 30-40 part;
3. reaction temperature rises to 80 ℃-90 ℃, adds the 1. 35%-45% of gained mixture of step again, reacts 30-60 minute; Again remaining step mixture is 1. added, add initator 1-3 part simultaneously, cationic active agent 15-25 part; Control temperature at 80-90 ℃, 2-3 hour;
4. be cooled to 55 ℃-50 ℃, add NaHSO
33-5 part is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
The preparation method of the siliceous gluing reinforcing agent of above-mentioned novel fluorine, step 2. take by weighing step 1. the gained mixture 40%, add 7 parts of initators; 35 parts of cationic active agents, step 3. reaction temperature rise to 80 ℃-90 ℃, add again step 1. the gained mixture 40%; Reacted 45 minutes, and more remaining step mixture was 1. added, add 2 parts of initators simultaneously; 20 parts of cationic active agents are controlled temperature at 80-90 ℃, 2.5 hours.
Adopt technique scheme, the present invention has following advantage: owing in the process of reaction copolymerization, added fluorine-containing siliceous initator, the dispersiveness of raising finished product, water-soluble.
Table 1 is the fluorine-containing siliceous reinforcing agent effect comparison analytical table of fluorine-containing reinforcing agent, siliceous reinforcing agent and the present invention.
Table 1
| Effect | Fluorine-containing reinforcing agent | Siliceous reinforcing agent | The present invention |
| Maturation period | 2-3 hour | 2-3 hour | Following machine slaking |
| Surface strength of paper | Generally | Generally | Improve 30% |
| Receive the systematic influence degree | Be prone to | Be prone to | Be prone to |
| The applying glue cost | 50 yuan/T paper | 50-55 unit/T paper | 25-30 unit/T paper |
| The cleaning of paper manufacturing systems | Well | Well | ? |
Analyzed by table 1, the present invention is the top sizing of paper, can reduce the applying glue cost, improves the surface strength of paper, shortens the maturation period, and sizing efficiency receives systematic influence less, and applying glue each item index is relatively stable, and can keep the cleaning of paper manufacturing systems.
The specific embodiment
Embodiment 1:
1. styrene 30-40 by weight; Acrylic acid ester 30-40; Any 4-15 in fluorochemical monomer methacrylic acid ten difluoro fat in heptan, methacrylic acid hexafluoro fourth fat or the methacrylic acid trifluoro second fat, any 5-10 in silicon-containing monomer VTES or VTES, vinyltrimethoxy silane, propyl trimethoxy silicane, the Y-propyl trimethoxy silicane.
Take by weighing each raw material, each raw materials mix is even;
2. take by weighing the 1. 35%-45% of gained mixture of step, adding initator is KPS, (NH
4)
2S
2O
8, KM
nO
4In any 6-8 part, any 30-40 part in cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride or 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or the palmityl propyl ammonium chloride;
3. reaction temperature rises to 80 ℃-90 ℃, adds the 1. 35%-45% of gained mixture of step again, reacts 30-60 minute; Again remaining step mixture is 1. added, add initator 1-3 part simultaneously, cationic active agent 15-25 part; Control temperature at 80-90 ℃, 2-3 hour;
4. be cooled to 55 ℃-50 ℃, add NaHSO
33-5 part is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 1: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 30kg, acrylic acid ester 30kg, fluorochemical monomer methacrylic acid ten difluoro fat in heptan 4kg and silicon-containing monomer VTES 5kg mixes; 2. take by weighing 35% of gained mixture, adding initator is KPS 6kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 30kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 35%, reacted 30 minutes, again with remaining step 1. mixture add; Add initator KPS1kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 15kg controls temperature at 80 ℃-90 ℃, 2 hours; 4. be cooled to 55 ℃, add NaHSO
33kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 2: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 31kg, acrylic acid ester 31kg, fluorochemical monomer methacrylic acid ten difluoro fat in heptan 4.5kg and silicon-containing monomer VTES 5.1kg mixes; 2. take by weighing 37% of gained mixture, adding initator is KPS 6.5kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 32kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 38%, reacted 35 minutes, again with remaining step 1. mixture add; Add initator KPS1.5kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 17kg controls temperature at 80-90 ℃, 2.5 hours; 4. be cooled to 53 ℃, add NaHSO
33.4kg, be cooled to normal temperature and make fluorine-containing siliceous gluing reinforcing agent.
Embodiment 3: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 35kg, acrylic acid ester 35kg, fluorochemical monomer methacrylic acid ten difluoro fat in heptan 7kg and silicon-containing monomer VTES 5.3kg mixes; 2. take by weighing 40% of gained mixture, adding initator is KPS7kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 35kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 40%, reacted 45 minutes, again with remaining step 1. mixture add; Add initator KPS2kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 20kg controls temperature at 80-90 ℃, 2.5 hours; 4. be cooled to 53 ℃, add NaHSO
34kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 4: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 39kg, acrylic acid ester 38kg, fluorochemical monomer methacrylic acid ten difluoro fat in heptan 10kg and silicon-containing monomer VTES 9kg mixes; 2. take by weighing 42% of gained mixture, adding initator is KPS7.5kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 38kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 43%, reacted 55 minutes, again with remaining step 1. mixture add; Add initator KPS2.5kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 23kg controls temperature at 80-90 ℃, 2.8 hours; 4. be cooled to 51 ℃, add NaHSO
34.5kg, be cooled to normal temperature and make fluorine-containing siliceous gluing reinforcing agent.
Embodiment 5: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 40kg, acrylic acid ester 40kg, fluorochemical monomer methacrylic acid ten difluoro fat in heptan 15kg and silicon-containing monomer VTES 10kg mixes; 2. take by weighing 45% of gained mixture, adding initator is KPS8kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 40kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 45%, reacted 60 minutes, again with remaining step 1. mixture add; Add initator KPS3kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 25kg controls temperature at 80-90 ℃, 3 hours; 4. be cooled to 50 ℃, add NaHSO
35kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 6: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 30kg, acrylic acid ester 30kg, fluorochemical monomer methacrylic acid hexafluoro fourth fat 4kg and silicon-containing monomer VTES 5kg mixes; 2. take by weighing 35% of gained mixture, adding initator is KPS6kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 30kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 35%, reacted 30 minutes, again with remaining step 1. mixture add; Add initator KPS1kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 15kg controls temperature at 80 ℃-90 ℃, 2 hours; 4. be cooled to 55 ℃, add NaHSO
33kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 7: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 31kg, acrylic acid ester 31kg, fluorochemical monomer methacrylic acid hexafluoro fourth fat 4.5kg and silicon-containing monomer VTES 5.1kg mixes; 2. take by weighing 37% of gained mixture, adding initator is KPS 6.5kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 32kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 38%, reacted 35 minutes, again with remaining step 1. mixture add; Add initator KPS1.5kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 17kg controls temperature at 80-90 ℃, 2.5 hours; 4. be cooled to 53 ℃, add NaHSO
33.4kg, be cooled to normal temperature and make fluorine-containing siliceous gluing reinforcing agent.
Embodiment 8: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 35kg, acrylic acid ester 35kg, fluorochemical monomer methacrylic acid hexafluoro fourth fat 7kg and silicon-containing monomer VTES 5.3kg mixes; 2. take by weighing 40% of gained mixture, adding initator is KPS7kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 35kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 40%, reacted 45 minutes, again with remaining step 1. mixture add; Add initator KPS2kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 20kg controls temperature at 80-90 ℃, 2.5 hours; 4. be cooled to 53 ℃, add NaHSO
34kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 9: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 39kg, acrylic acid ester 38kg, fluorochemical monomer methacrylic acid hexafluoro fourth fat 10kg and silicon-containing monomer VTES 9kg mixes; 2. take by weighing 42% of gained mixture, adding initator is KPS7.5kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 38kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 43%, reacted 55 minutes, again with remaining step 1. mixture add; Add initator KPS2.5kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 23kg controls temperature at 80-90 ℃, 2.8 hours; 4. be cooled to 51 ℃, add NaHSO
34.5kg, be cooled to normal temperature and make fluorine-containing siliceous gluing reinforcing agent.
Embodiment 10: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 40kg, acrylic acid ester 40kg, fluorochemical monomer methacrylic acid hexafluoro fourth fat 15kg and silicon-containing monomer VTES 10kg mixes; 2. take by weighing 45% of gained mixture, adding initator is KPS8kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 40kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 45%, reacted 60 minutes, again with remaining step 1. mixture add; Add initator KPS3kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 25kg controls temperature at 80-90 ℃, 3 hours; 4. be cooled to 50 ℃, add NaHSO
35kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 11: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 30kg, acrylic acid ester 30kg, fluorochemical monomer methacrylic acid trifluoro second fat 4kg and silicon-containing monomer VTES 5kg mixes; 2. take by weighing 35% of gained mixture, adding initator is KPS 6kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 30kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 35%, reacted 30 minutes, again with remaining step 1. mixture add; Add initator KPS1kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 15kg controls temperature at 80 ℃-90 ℃, 2 hours; 4. be cooled to 55 ℃, add NaHSO
33kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 12: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 31kg, acrylic acid ester 31kg, fluorochemical monomer methacrylic acid trifluoro second fat 4.5kg and silicon-containing monomer VTES 5.1kg mixes; 2. take by weighing 37% of gained mixture, adding initator is KPS 6.5kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 32kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 38%, reacted 35 minutes, again with remaining step 1. mixture add; Add initator KPS1.5kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 17kg controls temperature at 80-90 ℃, 2.5 hours; 4. be cooled to 53 ℃, add NaHSO
33.4kg, be cooled to normal temperature and make fluorine-containing siliceous gluing reinforcing agent.
Embodiment 13: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 35kg, acrylic acid ester 35kg, fluorochemical monomer methacrylic acid trifluoro second fat 7kg and silicon-containing monomer VTES 5.3kg mixes; 2. take by weighing 40% of gained mixture, adding initator is KPS7kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 35kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 40%, reacted 45 minutes, again with remaining step 1. mixture add; Add initator KPS2kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 20kg controls temperature at 80-90 ℃, 2.5 hours; 4. be cooled to 53 ℃, add NaHSO
34kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Embodiment 14: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 39kg, acrylic acid ester 38kg, fluorochemical monomer methacrylic acid trifluoro second fat 10kg and silicon-containing monomer VTES 9kg mixes; 2. take by weighing 42% of gained mixture, adding initator is KPS7.5kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 38kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 43%, reacted 55 minutes, again with remaining step 1. mixture add; Add initator KPS2.5kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 23kg controls temperature at 80-90 ℃, 2.8 hours; 4. be cooled to 51 ℃, add NaHSO
34.5kg, be cooled to normal temperature and make fluorine-containing siliceous gluing reinforcing agent.
Embodiment 15: the siliceous gluing reinforcing agent of a kind of novel fluorine, and got by the following steps preparation: 1. taking by weighing styrene 40kg, acrylic acid ester 40kg, fluorochemical monomer methacrylic acid trifluoro second fat 15kg and silicon-containing monomer VTES 10kg mixes; 2. take by weighing 45% of gained mixture, adding initator is KPS8kg, cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 40kg; 3. reaction temperature rises to 80 ℃-90 ℃; Add again step 1. the gained mixture 45%, reacted 60 minutes, again with remaining step 1. mixture add; Add initator KPS3kg simultaneously; Cationic active agent methylacryoyloxyethyl trimethyl ammonium chloride 25kg controls temperature at 80-90 ℃, 3 hours; 4. be cooled to 50 ℃, add NaHSO
35kg is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
Silicon-containing monomer can also be any in VTES, vinyltrimethoxy silane, propyl trimethoxy silicane or the Y-propyl trimethoxy silicane in the foregoing description.
Initator can also be (NH in the foregoing description
4)
2S
2O
8Or KM
nO
4, cationic active agent can also be any in methylacryoyloxyethyl trimethyl ammonium chloride or 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or the palmityl propyl ammonium chloride.
KPS described in the foregoing description is water miscible potassium peroxydisulfate.
Claims (3)
1. the preparation method of a fluorine-containing siliceous gluing reinforcing agent is characterized in that: comprise that the following step gathers:
1. take by weighing following raw material by weight: styrene 30-40, acrylic acid ester 30-40, fluorochemical monomer 4-15, silicon-containing monomer 5-10, initator 7-11 part, cationic active agent 45-65, with styrene, acrylic acid ester, fluorochemical monomer and silicon-containing monomer mix; Described initator is KPS, (NH
4)
2S
2O
8, KM
nO
4In any, cationic active agent is any in methylacryoyloxyethyl trimethyl ammonium chloride or 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or the palmityl propyl ammonium chloride; Said fluorochemical monomer is any in methacrylic acid ten difluoro fat in heptan, methacrylic acid hexafluoro fourth fat or the methacrylic acid trifluoro second fat, and silicon-containing monomer is any in VTES or VTES, vinyltrimethoxy silane, propyl trimethoxy silicane, the Y-propyl trimethoxy silicane;
2. take by weighing the 1. 35%-45% of gained mixture of step, add initator 6-8 part, cationic active agent 30-40 part;
3. reaction temperature rises to 80 ℃-90 ℃, adds the 1. 35%-45% of gained mixture of step again, reacts 30-60 minute; Again remaining step mixture is 1. added, add initator 1-3 part simultaneously, cationic active agent 15-25 part; Control temperature at 80-90 ℃, 2-3 hour;
4. be cooled to 55 ℃-50 ℃, add NaHSO
33-5 part is cooled to normal temperature and makes fluorine-containing siliceous gluing reinforcing agent.
2. the preparation method of fluorine-containing siliceous gluing reinforcing agent according to claim 1, it is characterized in that: the feedstock production by following weight portion forms: styrene 35, acrylic acid ester 35, fluorochemical monomer 7, silicon-containing monomer 5.3.
3. the preparation method of fluorine-containing siliceous gluing reinforcing agent according to claim 2 is characterized in that: step 2. take by weighing step 1. the gained mixture 40%, add 7 parts of initators; 35 parts of cationic active agents, step 3. reaction temperature rise to 80 ℃-90 ℃, add again step 1. the gained mixture 40%; Reacted 45 minutes, and more remaining step mixture was 1. added, add 2 parts of initators simultaneously; 20 parts of cationic active agents are controlled temperature at 80-90 ℃, 2.5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010187129XA CN101831842B (en) | 2010-05-31 | 2010-05-31 | Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010187129XA CN101831842B (en) | 2010-05-31 | 2010-05-31 | Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101831842A CN101831842A (en) | 2010-09-15 |
| CN101831842B true CN101831842B (en) | 2012-01-25 |
Family
ID=42716042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010187129XA Active CN101831842B (en) | 2010-05-31 | 2010-05-31 | Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101831842B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107675550A (en) * | 2017-10-10 | 2018-02-09 | 枣庄市恒宇纸业有限公司 | A kind of parchment and preparation method thereof |
| CN116446215B (en) * | 2023-03-22 | 2024-05-28 | 冠宏化工（扬州）有限公司 | Whitening sizing agent for papermaking and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281643C (en) * | 2002-06-17 | 2006-10-25 | 王存孝 | Silicofluoride containing acrylic copolyresin emulsion and paint |
| CN1557848A (en) * | 2004-01-15 | 2004-12-29 | 曹晓利 | Silicon-fluorin acrylic acid ternary polymerization latex and method for preparation thereof |
| CN100572408C (en) * | 2005-04-29 | 2009-12-23 | 广州宏昌胶粘带厂 | Single component room temperature crosslinked water fluoric resin emulsion and its production and application |
| CN100480461C (en) * | 2007-02-15 | 2009-04-22 | 浙江工业大学 | Method of preparing fluorine and silicon containing hydrophobic and oil repellent fabric finishing agent |
| EP2206735B1 (en) * | 2007-11-01 | 2012-03-21 | Asahi Glass Company, Limited | Fluorinated copolymer, water-proof and oil-proof agent composition, and their production methods |
-
2010
- 2010-05-31 CN CN201010187129XA patent/CN101831842B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101831842A (en) | 2010-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103333314B (en) | A kind of cationic photo-cured fluorine-containing urethane resin and preparation method thereof | |
| CN104774293B (en) | A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof | |
| CN113527592B (en) | Polycarboxylic acid water reducer for gypsum-based self-leveling mortar and preparation method and use method thereof | |
| CN105294958A (en) | Waterborne polyurethane modified acrylate emulsion preparation method | |
| CN101831842B (en) | Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof | |
| CN105855456A (en) | Curing agent of phosphate bonding agent self-hardening sand and preparation and using methods of curing agent of phosphate bonding agent self-hardening sand | |
| CN103276827B (en) | The preparation method of polyphenyl mortar warming plate and polyphenyl mortar | |
| CN107602781A (en) | A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer | |
| CN102718427B (en) | Sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof | |
| CN104387890B (en) | Modified polyurethane coating and preparation method thereof | |
| CN105236805A (en) | Polycarboxylic acid surface modified superfine stone powder and preparation method thereof | |
| CN103980431A (en) | Amphoteric polycarboxylic-acid water reducer and synthesis thereof | |
| CN105693942A (en) | Novel acrylic-based resin material applied to mineral-filled type polymer composite and production technology of novel acrylic-based resin material | |
| CN102352204A (en) | Preparation method for bonding material for energy-saving lamp | |
| CN102060964B (en) | Preparation method and application of amino acrylic resin | |
| CN106746854B (en) | A kind of concrete prefabricated bridge panel with plasticizer | |
| CN102352202A (en) | Method for preparing bonding material | |
| CN114195952B (en) | Early strength water reducer and preparation method and application thereof | |
| CN105295219A (en) | Polyvinyl chloride pipe and manufacturing method thereof | |
| CN112376279B (en) | Preparation method of impregnating compound for producing glass fiber continuous felt | |
| CN108384503A (en) | A kind of preparation method of the special adhesive of flexible face brick | |
| CN110436873B (en) | Inorganic cementing material applicable to 3D printing and preparation method thereof | |
| CN105949437A (en) | PU xanthochromia-resisting tripolymer curing agent formula and producing method | |
| CN105755865A (en) | Application of hyperbranched dyeing assistant to increasing of dyeability of superfine-fiber polyurethane synthetic leather | |
| CN106366236B (en) | The preparation method of PVC foam foaming control agent used for artificial leather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: LUOHE HR CHEMICAL INDUSTRY CO., LTD. Free format text: FORMER OWNER: LUOHE TIANMA CHEMICALS CO., LTD. Effective date: 20130225 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130225 Address after: 462000 No. 73 East Renmin Road, Henan, Luohe Patentee after: Luohe Hengrui Chemical Co., Ltd. Address before: 462000 No. 21, Hengshan Road, Henan, Luohe Patentee before: Luohe Tianma Chemicals Co., Ltd. |
|
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 462000 Henan Luohe economic and Technological Development Zone, Luo Road and Hengshan Road intersection Patentee after: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Address before: 462000 No. 73 East Renmin Road, Henan, Luohe Patentee before: Luohe Hengrui Chemical Co., Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof Effective date of registration: 20160510 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Registration number: 2016990000341 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20170616 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Registration number: 2016990000341 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof Effective date of registration: 20170616 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Registration number: 2017990000493 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20180130 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Registration number: 2017990000493 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof Effective date of registration: 20180130 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Registration number: 2018990000092 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20190228 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Registration number: 2018990000092 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof Effective date of registration: 20190307 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY CO., LTD. Registration number: 2019990000186 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20200409 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY Co.,Ltd. Registration number: 2019990000186 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof Effective date of registration: 20200413 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY Co.,Ltd. Registration number: Y2020980001452 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20210120 Granted publication date: 20120125 Pledgee: Bank of China Limited by Share Ltd. Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY Co.,Ltd. Registration number: Y2020980001452 |