CN105297431A - Modification method for flexible wollastonite fiber - Google Patents
Modification method for flexible wollastonite fiber Download PDFInfo
- Publication number
- CN105297431A CN105297431A CN201510720197.0A CN201510720197A CN105297431A CN 105297431 A CN105297431 A CN 105297431A CN 201510720197 A CN201510720197 A CN 201510720197A CN 105297431 A CN105297431 A CN 105297431A
- Authority
- CN
- China
- Prior art keywords
- wollastonite
- fiber
- flexible
- wollastonite fibre
- wollastonite fiber
- 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.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 113
- 239000010456 wollastonite Substances 0.000 title claims abstract description 107
- 229910052882 wollastonite Inorganic materials 0.000 title claims abstract description 107
- 238000002715 modification method Methods 0.000 title abstract 3
- 238000003756 stirring Methods 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 9
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 5
- 239000011490 mineral wool Substances 0.000 claims description 24
- 230000005855 radiation Effects 0.000 claims description 16
- 239000003093 cationic surfactant Substances 0.000 claims description 15
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 12
- 235000012241 calcium silicate Nutrition 0.000 claims description 12
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 12
- 230000001413 cellular effect Effects 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000006698 induction Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 230000005251 gamma ray Effects 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- QGFGLYOMJKJZIC-UHFFFAOYSA-N 2-dodecyl-1h-benzimidazole Chemical class C1=CC=C2NC(CCCCCCCCCCCC)=NC2=C1 QGFGLYOMJKJZIC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- MSTXYVOKCPMBJI-UHFFFAOYSA-N [Br-].[NH4+].CC(CCCCCCCCCCCCC)(C)C Chemical compound [Br-].[NH4+].CC(CCCCCCCCCCCCC)(C)C MSTXYVOKCPMBJI-UHFFFAOYSA-N 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 11
- 239000002557 mineral fiber Substances 0.000 abstract description 10
- 229920002873 Polyethylenimine Polymers 0.000 abstract 2
- 241001466460 Alveolata Species 0.000 abstract 1
- 210000003850 cellular structure Anatomy 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract 1
- 229920001444 polymaleic acid Polymers 0.000 abstract 1
- 150000003376 silicon Chemical class 0.000 description 21
- 239000011707 mineral Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the field of inorganic mineral fiber, and particularly relates to a modification method for flexible wollastonite fiber. The method is characterized by including the following steps of adding wollastonite fiber to a sodium hydroxide solution to be subjected to alkaline treatment so that the surfaces of wollastonite fiber can be of an alveolate cellular structure, adding polydimethylsiloxane and conducting stirring and mixing to obtain modified wollastonite fiber, making gamma rays irradiate the modified wollastonite fiber and polyethylene imine under the effect of initiator so that polyethylene imine and polymaleic acid can be subjected to a copolymerization reaction, grafting the mixture to the surfaces of the modified wollastonite fiber, adding positive ion surface modifier for surface wrapping, and obtaining flexible wollastonite fiber. By means of the modification method, the surface activity of wollastonite fiber can be improved, flexibility and dispersibility of wollastonite fiber are improved, the bonding force of wollastonite fiber and plant fiber is enhanced, and when flexible wollastonite fiber is used for papermaking, flexibility of paper can be obviously improved and paper can be good in hand feeling and light in weight.
Description
Technical field
The invention belongs to inorganic mineral fiber field, particularly a kind of method of modifying of flexible wollastonite fibre.
Background technology
Paper industry plays key player in global economy and civilization, and the output value accounts for 2.5% of the world industry gross output value, accounts for 2% of quantum of world trade.Timber is the main raw material of paper industry, accounts for more than 93% of paper making raw material, along with the fast development of paper-making industry, causes disafforestation on a large scale, and whole world area of woods is fallen sharply, and desertification aggravates, and also brings serious contaminated environment simultaneously, affects human health.Current China paper total amount is continuous, paper making raw material critical shortage, forces us actively to find the substitute of cheap paper pulp fiber.Because China has more rich mineral fibres resource, therefore replaced by mineral fibres Activities of Some Plants fiber to be used for papermaking, can not only production cost be reduced, and significant to protection China's Forest Resources.
Wollastonite fibre is a kind of chain calcium metasilicate mineral of natural output, there is high whiteness, preferably heat endurance and the feature such as chemical stability, higher draw ratio, show some characteristic of fiber, copy paper can be carried out theoretically as filler Substitute For Partial paper pulp fiber, not only production cost can be reduced, and significantly can alleviate the pressure of China's afforestation, reduce the felling of the forest reserves.Although wollastonite fibre can be combined with string, but because its fiber surface does not almost have to produce interactional group with plant fibre surface, combination between itself and string does not form Hydrogenbond, but due to its length than the large filling of common fillers between the fibers, it is strong that adhesion can not show a candle to adhesion between string, and it retains more in page, think larger to paper strength performance shadow.
Research shows to carry out to natural wollastonite mineral fiber the compatibility that surface modification can further improve wollastonite mineral fiber and string, alleviate the adverse effect that it produces paper making process and paper properties, give full play to the application advantage of its fibre-like morphology in paper production.As China Patent Publication No. CN103031761A discloses the preparation method of a kind of paper grade (stock) CATION wollastonite mineral fiber slurry, first wollastonite mine is carried out being pulverized and mixed with the composite modifier A be made up of cationic polyacrylamide and polyethylene glycol oxide and obtain elementary modified grammite mineral fibres, pulpous state mineral fibres is prepared into after adding appropriate water, add under stirring by PDDA, polymine, aluminum sulfate, aluminium polychloride composition composite modifier B and by diethylenetriamine, p-methyl benzenesulfonic acid, adipic acid, stearic acid, the modifier C of the synthesis such as epoxychloropropane and hydrochloric acid, after stirring paper grade (stock) CATION wollastonite mineral fiber slurry, effectively can not only improve the retention of mineral fibres in paper, also reduce the excessive interpolation of mineral fibres to the impact of paper strength simultaneously, improve the addition of mineral fibres in paper pulp, China Patent Publication No. CN102745909A discloses the low abrasion wollastonite mineral fiber of paper grade (stock), be made up of according to the ratio of weight and number of 1000:8 ~ 15:1 ~ 2 modified grammite, composite modifier and retention modifier, before using, it is mixed with slurry with water, makes composite modifier and retention modifier be coated on modified grammite surface completely.Paper grade (stock) of the present invention low abrasion wollastonite mineral fiber modified effect is obvious, not only can reduce the degree of wear of wollastonite to papermaking screen cloth, can also improve the retention of wollastonite mineral fiber in paper pulp simultaneously; China Patent Publication No. CN102249530A discloses a kind of wollastonite with high length-diameter ratio fiber and preparation method thereof, this fiber is made up of wollastonite and cation modifier, wollastonite on the surface hydroxyl activity with add cation modifier functional group its react, form cation group, to realize pulverizing, modification synchronously completes, greatly improve the whiteness of paper, flatness, opacity, printing quality, can maximum to 30% ratio substituted plant fiber, be effectively held in paper physical strength and reduce production cost.
In sum, method of modifying at present for wollastonite fibre mainly adopts cation modifier to carry out surface modification, although improve the compatibility of wollastonite fibre and string to a certain extent, improve the retention of mineral fibres in paper-making process, but because the active group on wollastonite mineral fiber surface is little, therefore with cation modifier in conjunction with limited, add the consumption of modifier, reduce the consumption of modifier; Meanwhile, being added on of simply cation-modified wollastonite fibre is improved into while paper ash divides, along with addition increase can to paper properties particularly intensity index produce adverse effect to a certain degree.
Summary of the invention
The present invention is directed to the problems referred to above, propose a kind of method of modifying of flexible wollastonite fibre.The method is joined in sodium hydroxide solution by wollastonite fibre to carry out basic treatment, make the cellular microcellular structure of wollastonite fibre surface presentation, form blemish, be conducive to the permeable reactive of modifier dimethyl silicone polymer, then under the effect of initator by gamma-ray irradiation process, polymine and poly are grafted to modified grammite fiber surface, increase the quantity of wollastonite fibre surface-active functional group, then add cationic surfactant and carry out Surface coating, make wollastonite fibre surface with a certain amount of positive charge, easily react with electronegative string generation charge neutrality, wollastonite fibre and string are combined closely.The flexible wollastonite fibre of the present invention has higher flexibility and dispersiveness, for significantly improving the pliability of paper during papermaking, makes that paper feel is good, light weight.
For achieving the above object, the present invention adopts following technical scheme:
A method of modifying for flexible wollastonite fibre, is characterized in that comprising the following steps:
(1) wollastonite of 60 ~ 80 weight portions being added mass fraction is stir 30 ~ 50min in the sodium hydroxide solution of 1.5-2%, make the cellular microcellular structure of wollastonite fibre surface presentation, then filter, add the dimethyl silicone polymer of 5 ~ 15 weight portions, continue stirring 20 ~ 30min, obtain modified silicon ash mineral wool;
(2) put in airtight stirred autoclave by the modified silicon ash mineral wool obtained in step (1), the poly adding the polymine of 5 ~ 10 weight portions and 5 ~ 10 weight portions stirs 5 ~ 10min, make wollastonite fibre and mixed with polymers even; Mixture is placed in the gamma Rays device that radiation dose rate is 3 ~ 10kGy/h, add the initator of 1 ~ 5 weight portion, utilize the process of induction system dynamic radioaction, make polymine and poly generation copolyreaction, and be grafted to the surface of the wollastonite fibre after surface modification;
(3) the modified silicon ash mineral wool obtained in step (3) is added in the water of its 50 ~ 70 times of weight, 15 ~ 30min is stirred in 40 ~ 60 DEG C, the cationic surfactant of 1 ~ 10 weight portion is added under stirring, continue stirring 20 ~ 30min, cationic surfactant is made to be coated on modified grammite fiber surface completely, filter, dry, obtain a kind of flexible wollastonite fibre.
Wollastonite described in above-mentioned steps (1) is the wollastonite with raphioid fiber crystal structure, by the alkaline solution treatment of appropriate concentration, the fibre structure surface of wollastonite is intact, fiber uniform elongate, and fiber surface is dispersed with intensive linear micropore, make wollastonite fibre surface presentation cellular, reduce the smoothness of fiber surface, be conducive to the permeable reactive of modifier.
Initator described in above-mentioned steps (2) is at least one in 1-METHYLPYRROLIDONE, NVP, polyvinylpyrrolidone.
Gamma Rays device described in above-mentioned steps (2) adopts co-60 radiation source apparatus, and gamma-ray dosage of radiation is 30 ~ 100kGy.Under gamma-rays effect, Si-O-Si key in wollastonite fibre ruptures, with the active function groups generation chemical bonding of dimethyl silicone polymer, be easy to polymine and the reaction of poly generation copolymerized grafting, the active function groups quantity on wollastonite fibre surface is increased, increase the distance of fiber molecule interchain simultaneously, weaken the active force between fiber molecule, reach and increase flexible object.
Cationic surfactant described in above-mentioned steps (3) is at least one in cationic starch, dimethyl stearyl allyl ammonium chloride, DTAB, trimethyl n-tetradecane ammonium bromide, dodecyl benzo imidazoles, by cationic surfactant, Surface coating is carried out to modified silicon ash mineral wool, make wollastonite fibre surface with a certain amount of positive charge, easily react with electronegative string generation charge neutrality, wollastonite fibre and string are combined closely.
The method of modifying of a kind of flexible silicon lime stone of the present invention, wollastonite fibre is joined in sodium hydroxide solution and carry out basic treatment, make the cellular microcellular structure of wollastonite fibre surface presentation, form blemish, make surface functional group more exposed, strengthen the reactivity of it and macromolecule organic, be conducive to the permeable reactive of modifier dimethyl silicone polymer, then under the effect of initator by gamma-ray irradiation process, Si-O-Si key in wollastonite fibre ruptures, with the active function groups generation chemical bonding of dimethyl silicone polymer, be easy to polymine and the reaction of poly generation copolymerized grafting, increase the active group on wollastonite fibre surface, increase the distance of fiber molecule interchain simultaneously, weaken the active force between fiber molecule, improve pliability and the intensity of wollastonite fibre, add cationic surfactant simultaneously and Surface coating is carried out to modified silicon ash mineral wool, make fiber surface with certain positive charge, easily react with electronegative string generation charge neutrality, wollastonite fibre and string are combined closely, greatly improves the application performance of wollastonite fibre for paper technology.
The method of modifying of a kind of flexible silicon lime stone of the present invention, compared with prior art outstanding feature and useful effect are:
1, the preparation method of a kind of flexible wollastonite fibre of the present invention, first carries out basification to wollastonite fibre, makes fiber surface present cellular microcellular structure, makes surface functional group more exposed, is conducive to the permeable reactive of modifier; Then gamma Rays process is utilized, Si-O-Si key in wollastonite fibre ruptures, with the active function groups generation chemical bonding of dimethyl silicone polymer, be easy to polymine and the reaction of poly generation copolymerized grafting, the active function groups quantity on wollastonite fibre surface is increased, improve the pliability of wollastonite fibre, easily combine closely with electronegative string, improve the utilization rate of wollastonite fibre in paper industry.
2, the preparation method of a kind of flexible wollastonite fibre of the present invention, also add cationic surfactant and Surface coating is carried out to modified silicon ash mineral wool, make wollastonite fibre surface with a certain amount of positive charge, easily react with electronegative string generation charge neutrality, wollastonite fibre and string are combined closely, improves its consumption as papermaking filler.
3, the flexible wollastonite fibre pliability prepared of the present invention is good, and the paper surface manufactured with it is smooth, and pliability significantly improves, and string can be replaced as the raw material of papermaking.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is explained in detail, is not restricted to the present invention.When not departing from said method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or improvement, all should be included within protection scope of the present invention.
embodiment 1
(1) wollastonite of 60 weight portions being added mass fraction is stir 50min in the sodium hydroxide solution of 1.5%, make the cellular microcellular structure of wollastonite fibre surface presentation, then filter, add the dimethyl silicone polymer of 10 weight portions, continue to stir 30min, obtain modified silicon ash mineral wool;
(2) put in airtight stirred autoclave by the modified silicon ash mineral wool obtained in step (1), the poly adding the polymine of 10 weight portions and 10 weight portions stirs 10min, make wollastonite fibre and mixed with polymers even; Mixture is placed in the gamma Rays device that radiation dose rate is 3 ~ 10kGy/h, add the 1-METHYLPYRROLIDONE of 5 weight portions, utilize the process of induction system dynamic radioaction, dosage of radiation is 30kGy, make polymine and poly generation copolyreaction, and be grafted to the surface of the wollastonite fibre after surface modification;
(3) the modified silicon ash mineral wool obtained in step (3) is added in the water of its 70 times of weight, 30min is stirred in 60 DEG C, the cationic starch of 5 weight portions is added under stirring, continue to stir 20min, cationic surfactant is made to be coated on modified grammite fiber surface completely, filter, dry, obtain a kind of flexible wollastonite fibre.
embodiment 2
(1) wollastonite of 70 weight portions being added mass fraction is stir 30min in the sodium hydroxide solution of 2%, make the cellular microcellular structure of wollastonite fibre surface presentation, then filter, add the dimethyl silicone polymer of 10 weight portions, continue to stir 30min, obtain modified silicon ash mineral wool;
(2) put in airtight stirred autoclave by the modified silicon ash mineral wool obtained in step (1), the poly adding the polymine of 5 weight portions and 5 weight portions stirs 10min, make wollastonite fibre and mixed with polymers even; Mixture is placed in the gamma Rays device that radiation dose rate is 3 ~ 10kGy/h, add the NVP of 3 weight portions, utilize the process of induction system dynamic radioaction, dosage of radiation is 50kGy, make polymine and poly generation copolyreaction, and be grafted to the surface of the wollastonite fibre after surface modification;
(3) the modified silicon ash mineral wool obtained in step (3) is added in the water of its 50 times of weight, 15min is stirred in 40 DEG C, the dimethyl stearyl allyl ammonium chloride of 7 weight portions is added under stirring, continue to stir 30min, cationic surfactant is made to be coated on modified grammite fiber surface completely, filter, dry, obtain a kind of flexible wollastonite fibre.
embodiment 3
(1) wollastonite of 80 weight portions being added mass fraction is stir 50min in the sodium hydroxide solution of 2%, make the cellular microcellular structure of wollastonite fibre surface presentation, then filter, add the dimethyl silicone polymer of 5 weight portions, continue to stir 30min, obtain modified silicon ash mineral wool;
(2) put in airtight stirred autoclave by the modified silicon ash mineral wool obtained in step (1), the poly adding the polymine of 5 weight portions and 5 weight portions stirs 5 ~ 10min, make wollastonite fibre and mixed with polymers even; Mixture is placed in the gamma Rays device that radiation dose rate is 3 ~ 10kGy/h, add the polyvinylpyrrolidone of 1 weight portion, utilize the process of induction system dynamic radioaction, dosage of radiation is 30kGy, make polymine and poly generation copolyreaction, and be grafted to the surface of the wollastonite fibre after surface modification;
(3) the modified silicon ash mineral wool obtained in step (3) is added in the water of its 70 times of weight, 30min is stirred in 60 DEG C, the DTAB of 4 weight portions is added under stirring, continue to stir 20min, cationic surfactant is made to be coated on modified grammite fiber surface completely, filter, dry, obtain a kind of flexible wollastonite fibre.
embodiment 4
(1) wollastonite of 70 weight portions being added mass fraction is stir 40min in the sodium hydroxide solution of 2%, make the cellular microcellular structure of wollastonite fibre surface presentation, then filter, add the dimethyl silicone polymer of 10 weight portions, continue to stir 25min, obtain modified silicon ash mineral wool;
(2) put in airtight stirred autoclave by the modified silicon ash mineral wool obtained in step (1), the poly adding the polymine of 5 weight portions and 10 weight portions stirs 5min, make wollastonite fibre and mixed with polymers even; Mixture is placed in the gamma Rays device that radiation dose rate is 3 ~ 10kGy/h, add the 1-METHYLPYRROLIDONE of 2 weight portions, utilize the process of induction system dynamic radioaction, dosage of radiation is 40kGy, make polymine and poly generation copolyreaction, and be grafted to the surface of the wollastonite fibre after surface modification;
(3) the modified silicon ash mineral wool obtained in step (3) is added in the water of its 70 times of weight, 30min is stirred in 60 DEG C, the trimethyl n-tetradecane ammonium bromide of 3 weight portions is added under stirring, continue to stir 20min, cationic surfactant is made to be coated on modified grammite fiber surface completely, filter, dry, obtain a kind of flexible wollastonite fibre.
embodiment 5
(1) wollastonite of 60 weight portions being added mass fraction is stir 30 ~ 50min in the sodium hydroxide solution of 1.5-2%, make the cellular microcellular structure of wollastonite fibre surface presentation, then filter, add the dimethyl silicone polymer of 10 weight portions, continue stirring 20 ~ 30min, obtain modified silicon ash mineral wool;
(2) put in airtight stirred autoclave by the modified silicon ash mineral wool obtained in step (1), the poly adding the polymine of 10 weight portions and 5 weight portions stirs 10min, make wollastonite fibre and mixed with polymers even; Mixture is placed in the gamma Rays device that radiation dose rate is 3 ~ 10kGy/h, add the polyvinylpyrrolidone of 5 weight portions, utilize the process of induction system dynamic radioaction, dosage of radiation is 100kGy, make polymine and poly generation copolyreaction, and be grafted to the surface of the wollastonite fibre after surface modification;
(3) the modified silicon ash mineral wool obtained in step (3) is added in the water of its 70 times of weight, 30min is stirred in 60 DEG C, the dodecyl benzo imidazoles of 10 weight portions is added under stirring, continue to stir 30min, cationic surfactant is made to be coated on modified grammite fiber surface completely, filter, dry, obtain a kind of flexible wollastonite fibre.
Claims (5)
1. a method of modifying for flexible wollastonite fibre, is characterized in that comprising the following steps:
(1) wollastonite of 60 ~ 80 weight portions being added mass fraction is stir 30 ~ 50min in the sodium hydroxide solution of 1.5-2%, make the cellular microcellular structure of wollastonite fibre surface presentation, then filter, add the dimethyl silicone polymer of 5 ~ 15 weight portions, continue stirring 20 ~ 30min, obtain modified silicon ash mineral wool;
(2) put in airtight stirred autoclave by the modified silicon ash mineral wool obtained in step (1), the poly adding the polymine of 5 ~ 10 weight portions and 5 ~ 10 weight portions stirs 5 ~ 10min, make wollastonite fibre and mixed with polymers even; Mixture is placed in the gamma Rays device that radiation dose rate is 3 ~ 10kGy/h, add the initator of 1 ~ 5 weight portion, utilize the process of induction system dynamic radioaction, make polymine and poly generation copolyreaction, and be grafted to the surface of the wollastonite fibre after surface modification;
(3) the modified silicon ash mineral wool obtained in step (3) is added in the water of its 50 ~ 70 times of weight, 15 ~ 30min is stirred in 40 ~ 60 DEG C, the cationic surfactant of 1 ~ 10 weight portion is added under stirring, continue stirring 20 ~ 30min, cationic surfactant is made to be coated on modified grammite fiber surface completely, filter, dry, obtain a kind of flexible wollastonite fibre.
2. the method for modifying of a kind of flexible wollastonite fibre according to claim 1, is characterized in that the wollastonite described in step (1) is the wollastonite with raphioid fiber crystal structure.
3. the method for modifying of a kind of flexible wollastonite fibre according to claim 1, is characterized in that the initator described in step (2) is at least one in 1-METHYLPYRROLIDONE, NVP, polyvinylpyrrolidone.
4. the method for modifying of a kind of flexible wollastonite fibre according to claim 1, it is characterized in that the gamma Rays device described in step (2) adopts co-60 radiation source apparatus, gamma-ray dosage of radiation is 30 ~ 100kGy.
5. the method for modifying of a kind of flexible wollastonite fibre according to claim 1, is characterized in that the cationic surfactant described in step (3) is at least one in cationic starch, dimethyl stearyl allyl ammonium chloride, DTAB, trimethyl n-tetradecane ammonium bromide, dodecyl benzo imidazoles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510720197.0A CN105297431B (en) | 2015-10-30 | 2015-10-30 | A kind of method of modifying of flexible wollastonite fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510720197.0A CN105297431B (en) | 2015-10-30 | 2015-10-30 | A kind of method of modifying of flexible wollastonite fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105297431A true CN105297431A (en) | 2016-02-03 |
| CN105297431B CN105297431B (en) | 2017-12-12 |
Family
ID=55195202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510720197.0A Active CN105297431B (en) | 2015-10-30 | 2015-10-30 | A kind of method of modifying of flexible wollastonite fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105297431B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835697A (en) * | 2017-01-04 | 2017-06-13 | 酒泉恒通节能科技有限公司 | A kind of high-performance mineral fabric softening and preparation method thereof |
| CN113308936A (en) * | 2021-05-26 | 2021-08-27 | 六盘水师范学院 | Preparation method of natural mineral fiber/plant fiber degradable agricultural mulching film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070276082A1 (en) * | 2006-05-24 | 2007-11-29 | Kim Balfour | Poly(arylene ether) composition, method, and article |
| CN104448388A (en) * | 2014-11-03 | 2015-03-25 | 成都新柯力化工科技有限公司 | Special calcium metasilicate fiber for rich mineral paper and preparation method of special calcium metasilicate fiber |
| CN104626438A (en) * | 2014-12-30 | 2015-05-20 | 成都新柯力化工科技有限公司 | Method for preparing fiber stone paper |
-
2015
- 2015-10-30 CN CN201510720197.0A patent/CN105297431B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070276082A1 (en) * | 2006-05-24 | 2007-11-29 | Kim Balfour | Poly(arylene ether) composition, method, and article |
| CN104448388A (en) * | 2014-11-03 | 2015-03-25 | 成都新柯力化工科技有限公司 | Special calcium metasilicate fiber for rich mineral paper and preparation method of special calcium metasilicate fiber |
| CN104626438A (en) * | 2014-12-30 | 2015-05-20 | 成都新柯力化工科技有限公司 | Method for preparing fiber stone paper |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835697A (en) * | 2017-01-04 | 2017-06-13 | 酒泉恒通节能科技有限公司 | A kind of high-performance mineral fabric softening and preparation method thereof |
| CN106835697B (en) * | 2017-01-04 | 2019-09-20 | 酒泉恒通节能科技有限公司 | A kind of high-performance mineral fabric softening and preparation method thereof |
| CN113308936A (en) * | 2021-05-26 | 2021-08-27 | 六盘水师范学院 | Preparation method of natural mineral fiber/plant fiber degradable agricultural mulching film |
| CN113308936B (en) * | 2021-05-26 | 2022-07-08 | 六盘水师范学院 | Preparation method of natural mineral fiber/plant fiber degradable agricultural mulching film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105297431B (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105544206A (en) | A modifying method of soft wollastonite fibers | |
| FI70954C (en) | FOER FARING FRAMSTAELLNING AV PAPPER | |
| CN105239451B (en) | A kind of preparation method of paper grade (stock) mineral fibres | |
| RU2011115803A (en) | FILLER COMPOSITION | |
| Fan et al. | Starch-sodium stearate complex modified PCC filler and its application in papermaking | |
| CN104508202A (en) | Manufacture and use of composite structure containing precipitated carbonate | |
| CN105586803A (en) | Method for preparing network gel modified talcum powder special for papermaking | |
| CN105061774B (en) | A kind of paper making intensifier and preparation method thereof | |
| CA2550261A1 (en) | Filler for papermaking process | |
| CN105297431A (en) | Modification method for flexible wollastonite fiber | |
| CN105332277A (en) | Sepiolite fiber special for paper making and preparing method thereof | |
| CN101863650B (en) | Lime bamboo pulp fiber reinforced calcium silicate board | |
| CN102677533A (en) | Two-side offset paper | |
| CN102191720A (en) | Method for producing paper wet-strength agent with polyamide polyamine epichlorohydrin resin | |
| KR101535522B1 (en) | Preparation method of filler containing cellulose and the paper containing the filler thereby | |
| Zhang et al. | A facile and small-molecule regulated borate network gelation to improve the mildew proof, fire-retardant of bamboo | |
| CN105568677A (en) | Flexible modification method for microfine inorganic fibers for papermaking | |
| CN106638124B (en) | A kind of method of modifying improving ash content of paper and paper strength during starch conversion high concentration filler | |
| CN110172851A (en) | A kind of method of modifying producing wrapping paper chemi-mechanical pulp | |
| CN102517979B (en) | Dalle body paper and making method thereof | |
| CN105297433B (en) | A kind of gypsum fiber flexible modifying agent and preparation method thereof | |
| CN109629333A (en) | A kind of filler pre-treatment method for paper technology | |
| CN1965024A (en) | Gelled starch compositions and methods of making gelled starch compositions | |
| CN106147619A (en) | A kind of high printing opacity composite fireproof glass | |
| CN104018395B (en) | A kind of filler mixed liquor and preparation method thereof, the manufacture method of paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170721 Address after: 510640 Guangdong City, Tianhe District Province, No. five, road, public education building, unit 371-1, unit 2401 Applicant after: Guangdong Gaohang Intellectual Property Operation Co., Ltd. Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Applicant before: Chengdu Xinkeli Chemical Sci-Tech Co., Ltd. |
|
| CB03 | Change of inventor or designer information |
Inventor after: Guo Tao Inventor before: Chen Qing Inventor before: Sun Lizhi |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171025 Address after: 221400 north side of Mount Huangshan Road, Wuxi Industrial Zone, Xinyi, Xuzhou, Jiangsu, Xinyi Applicant after: Jiangsu tin Yi High-tech Zone Technology Development Co. Ltd. Address before: 510640 Guangdong City, Tianhe District Province, No. five, road, public education building, unit 371-1, unit 2401 Applicant before: Guangdong Gaohang Intellectual Property Operation Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180607 Address after: 221400 8 Taishan Road, Xiyi high tech Zone, Xinyi, Xuzhou, Jiangsu Patentee after: Jiangsu Kang Cheng new material Science and Technology Ltd. Address before: 221400 Wuxi, Xinyi Industrial Park, Wuxi Town, Xinyi, Xuzhou, Jiangsu Patentee before: Jiangsu tin Yi High-tech Zone Technology Development Co. Ltd. |
|
| TR01 | Transfer of patent right |