CN103724437A - Multifunctional guanidine salt grafted carboxymethyl cellulose paper-making additive and preparation method thereof - Google Patents
Multifunctional guanidine salt grafted carboxymethyl cellulose paper-making additive and preparation method thereof Download PDFInfo
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- CN103724437A CN103724437A CN201410010244.8A CN201410010244A CN103724437A CN 103724437 A CN103724437 A CN 103724437A CN 201410010244 A CN201410010244 A CN 201410010244A CN 103724437 A CN103724437 A CN 103724437A
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Abstract
The invention discloses a multifunctional guanidine salt grafted carboxymethyl cellulose paper making additive and a preparation method thereof. The preparation method comprises the following steps: adding carboxymethyl cellulose into sodium periodate solution, heating the mixture solution to react for 6h, filtering, washing and drying the reaction products to obtain dialdehyde carboxymethyl cellulose; dispersing the dialdehyde carboxymethyl cellulose in distilled water, adding guanidine salt into the mixture solution to react for 4h at certain temperature, filtering, washing and drying the reaction products to obtain the guanidine salt grafted carboxymethyl cellulose; coating the surface of paper sheet with the guanidine salt grafted carboxymethyl cellulose to prepare a high-strength and high-antibacterial-property functional paper. The surface of the paper sheet is coated with the multifunctional guanidine salt grafted carboxymethyl cellulose paper making additive, so that the paper sheet simultaneously has high strength and high antibacterial property, two main defects of the existing paper sheet such as low strength and low antibacterial property are conquered, and furthermore the multifunctional guanidine salt grafted carboxymethyl cellulose paper making additive has higher practical value.
Description
Technical field
The present invention relates to one for paper grade (stock) multifunctional assistant, specifically, relate to multi-functional paper making additive of a kind of guanidinesalt grafting carboxymethyl cellulose and preparation method thereof.
Background technology
In paper industry, carboxymethyl cellulose occupies an important position.Carboxymethyl cellulose can be used for wet end to be added, and can play the effects such as enhancing; For the top sizing of paper, can improve the surface strength of paper and improve printing performance; For painting processing paper, can improve printing performance and the printing effect of paper.In addition, carboxymethyl cellulose have aboundresources, low price, supply stable, easy to use, can chemical modification and the advantage such as biological degradation.Therefore, carboxymethyl cellulose and derivative product thereof are widely used in paper industry.Because carboxymethyl cellulose itself is without any anti-microbial effect, can not give paper anti-microbial property, therefore, using after carboxymethyl cellulose, easily cause bacteria breed and breeding in paper, thereby harm people's is healthy.
Summary of the invention
The object of the invention is to improve the deficiency of carboxymethyl cellulose without anti-microbial property itself, multi-functional paper making additive of a kind of novel guanidinesalt grafting carboxymethyl cellulose and preparation method thereof is provided.
For realizing object of the present invention, the technical scheme adopting is: the preparation method of the multi-functional paper making additive of a kind of guanidinesalt grafting carboxymethyl cellulose of the present invention, comprises the steps:
(1) carboxymethyl cellulose is joined in 0.1-10mol/L sodium periodate solution, reacting by heating under 30-80 ° of C, obtains dialdehyde carboxymethyl cellulose after product is filtered, washs and be dried; The mol ratio of described sodium periodate and carboxymethyl cellulose is 1:1-5;
(2) step (1) gained dialdehyde carboxymethyl cellulose is dispersed in distilled water, adds guanidinesalt and react under 30-80 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt grafting carboxymethyl cellulose; The mol ratio of described guanidinesalt and dialdehyde carboxymethyl cellulose is 1:1-20.Its synthetic chemistry formula figure is shown in Fig. 1.
The volumetric molar concentration of the above-mentioned sodium periodate solution of the present invention is 1 mol/L preferably; The mol ratio of described sodium periodate and carboxymethyl cellulose is preferably 1:1-2; The mol ratio of described guanidinesalt and dialdehyde carboxymethyl cellulose is preferably 1:1-12.
Guanidinesalt of the present invention can be Walaphage, Guanidinium hydrochloride etc., preferably Guanidinium hydrochloride.
The multi-functional paper making additive of guanidinesalt grafting carboxymethyl cellulose of the present invention is to be prepared from by above-mentioned the inventive method.
With respect to prior art, tool of the present invention has the following advantages:
China's paper industry is just experiencing raw material of papermaking fiber, paper product specification of quality, the adjustment of paper product kind, paper technology and equipment, and carboxymethyl cellulose has become paper industry one of the indispensable papermaking chemical product that improves the quality of products, reduces production costs.But utilize antiseptic-germicide modified carboxy methyl cellulose, make carboxymethyl cellulose there is high-efficiency antimicrobial performance and have not been reported.The present invention is directed to the deficiency of current carboxymethyl cellulose without anti-microbial property itself, first utilize sodium periodate that carboxymethyl cellulose is oxidized to dialdehyde carboxymethyl cellulose, by schiff base reaction, guanidinesalt is grafted on dialdehyde carboxymethyl cellulose again, thereby make carboxymethyl cellulose there is anti-microbial property, finally this modified carboxy methyl cellulose is applied to paper surface, thereby when improving paper tensile strength, also can give paper high-efficiency antimicrobial performance.
Accompanying drawing explanation
Fig. 1 is the chemical equation figure of the multi-functional paper making additive of guanidinesalt grafting carboxymethyl cellulose prepared of the embodiment of the present invention 1.
Fig. 2 is the infrared spectrogram of former carboxymethyl cellulose and guanidinesalt grafting carboxymethyl cellulose.
Fig. 3 is that the coating of guanidinesalt grafting carboxymethyl cellulose is on the figure that affects of paper strength.
Fig. 4 is body paper and the anti-microbial property comparison diagram of White Board to intestinal bacteria (a) and staphylococcus (b), and figure (a) is intestinal bacteria anti-microbial property figure, and figure (b) is staphylococcus anti-microbial property figure.
Embodiment
Below in conjunction with embodiment, the inventive method is described in further detail.It should be noted that, protection scope of the present invention should include but not limited to the disclosed technology contents of the present embodiment.
Embodiment 1
(1) carboxymethyl cellulose is joined in 1 mol/L sodium periodate solution, reacting by heating 6h under 30 ° of C, obtains dialdehyde carboxymethyl cellulose after product is filtered, washs and be dried; The mol ratio of described sodium periodate and carboxymethyl cellulose is 1:1.
(2) step (1) gained dialdehyde carboxymethyl cellulose is dispersed in distilled water, adds Guanidinium hydrochloride and react 4h under 30 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt grafting carboxymethyl cellulose; The mol ratio of described guanidinesalt and dialdehyde carboxymethyl cellulose is 1:1.
(1) carboxymethyl cellulose is joined in 1.5 mol/L sodium periodate solutions, reacting by heating 6h under 40 ° of C, obtains dialdehyde carboxymethyl cellulose after product is filtered, washs and be dried; The mol ratio of described sodium periodate and carboxymethyl cellulose is 1:1.2.
(2) step (1) gained dialdehyde carboxymethyl cellulose is dispersed in distilled water, adds Guanidinium hydrochloride and react 4h under 50 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt grafting carboxymethyl cellulose; The mol ratio of described guanidinesalt and dialdehyde carboxymethyl cellulose is 1:5.
Embodiment 3
(1) carboxymethyl cellulose is joined in 2 mol/L sodium periodate solutions, reacting by heating 6h under 50 ° of C, obtains dialdehyde carboxymethyl cellulose after product is filtered, washs and be dried; The mol ratio of described sodium periodate and carboxymethyl cellulose is 1:1.5.
(2) step (1) gained dialdehyde carboxymethyl cellulose is dispersed in distilled water, and adds Walaphage to react 4h under 60 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt grafting carboxymethyl cellulose; The mol ratio of described guanidinesalt and dialdehyde carboxymethyl cellulose is 1:10.
Embodiment 4
Performance test:
1, the intensity detection of White Board
Guanidinesalt grafting carboxymethyl cellulose prepared by embodiment 1.By the infrared spectra Fig. 2 to guanidinesalt grafting carboxymethyl cellulose and former carboxymethyl cellulose, analyze contrast known, in the infrared spectra of guanidinesalt grafting carboxymethyl cellulose, occur new absorption peak 1598cm
-1(N-H flexural vibration), show that guanidinesalt is successfully grafted on carboxymethyl cellulose.
Guanidinesalt grafting carboxymethyl cellulose prepared by embodiment 1 is applied to paper surface, and the intensity of White Board is measured, result as shown in Figure 3, in figure: DCMC-2, DCMC-4, DCMC-7, DCMC-8, DCMC-12 refer to respectively guanidinesalt grafting carboxymethyl cellulose (guanidinesalt grafting amount is respectively 2,4,7,8,12%).Can find out, because modified carboxy methyl cellulose has much amino, hydroxyl and carboxyl, in drying process, hydroxyl easy and paper fibre forms hydrogen bonded, thereby paper is had to good enhancement, when adding coating DCMC-7, the tensile index of paper increases to 72.38 Nm/g from 60.2, has improved 20%.
2, the anti-microbial property of White Board detects
For the multi-functional paper making additive of explanation the present invention's novel guanidinesalt grafting carboxymethyl cellulose is for the anti-microbial property after Paper Coating, measure the anti-microbial property of body paper and White Board.
After utilizing the multi-functional paper making additive of novel guanidinesalt grafting carboxymethyl cellulose prepared by embodiment 1 to be coated with paper, White Board and body paper are detected the inhibition of intestinal bacteria and streptococcus aureus respectively, as shown in Figure 4, DCMC-2, DCMC-4, DCMC-7, DCMC-8, DCMC-12 refer to respectively guanidinesalt grafting carboxymethyl cellulose (guanidinesalt grafting amount is respectively 2,4,7,8,12%) to result.Can find out, compared with body paper, the White Board that has been coated with the multi-functional paper making additive of guanidinesalt grafting carboxymethyl cellulose has obvious inhibition zone, and therefore the multi-functional paper making additive of this novel guanidinesalt grafting carboxymethyl cellulose has good anti-microbial property to paper.
Claims (4)
1. a preparation method for the multi-functional paper making additive of guanidinesalt grafting carboxymethyl cellulose, is characterized in that comprising the steps:
(1) carboxymethyl cellulose is joined in 0.1-10mol/L sodium periodate solution, reacting by heating under 30-80 ° of C, obtains dialdehyde carboxymethyl cellulose after product is filtered, washs and be dried; The mol ratio of described sodium periodate and carboxymethyl cellulose is 1:1-5;
(2) step (1) gained dialdehyde carboxymethyl cellulose is dispersed in distilled water, adds guanidinesalt and react under 30-80 ° of C, after product is filtered, washs and be dried, obtain guanidinesalt grafting carboxymethyl cellulose; The mol ratio of described guanidinesalt and dialdehyde carboxymethyl cellulose is 1:1-20.
2. the preparation method of the multi-functional paper making additive of guanidinesalt grafting carboxymethyl cellulose according to claim 1, is characterized in that: the volumetric molar concentration of described sodium periodate solution is 1 mol/L; The mol ratio of described sodium periodate and carboxymethyl cellulose is 1:1-2; The mol ratio of described guanidinesalt and dialdehyde carboxymethyl cellulose is 1:1-12.
3. the preparation method of the multi-functional paper making additive of guanidinesalt grafting carboxymethyl cellulose according to claim 1 and 2, is characterized in that: described guanidinesalt is selected from Walaphage or Guanidinium hydrochloride, preferably Guanidinium hydrochloride.
4. the multi-functional paper making additive of guanidinesalt grafting carboxymethyl cellulose, is characterized in that being prepared from by the method described in claim 1 or 2 or 3.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106280236A (en) * | 2016-08-26 | 2017-01-04 | 繁昌县倍思生产力促进中心有限公司 | A kind of wear-resistant antibacterial warming plate used for building exterior wall |
| CN106279858A (en) * | 2016-08-30 | 2017-01-04 | 安徽蓝德集团股份有限公司 | A kind of good coal mine cable protective cover material of antibacterial mechanical property |
| CN106317905A (en) * | 2016-08-30 | 2017-01-11 | 安徽蓝德集团股份有限公司 | Coal mine cable sheath material with excellent heat stability |
| CN106365584A (en) * | 2016-08-26 | 2017-02-01 | 繁昌县倍思生产力促进中心有限公司 | Preparation method of wear-proof insulation board for building external walls |
| CN106431102A (en) * | 2016-08-26 | 2017-02-22 | 繁昌县倍思生产力促进中心有限公司 | Phenolic foam heat-insulation board for external walls of buildings |
| CN107047992A (en) * | 2017-05-03 | 2017-08-18 | 丁永胜 | A kind of nutritious sheep feed |
| CN107087714A (en) * | 2017-05-03 | 2017-08-25 | 丁永胜 | A kind of high digestibility feed for sheep |
| CN107137749A (en) * | 2017-05-23 | 2017-09-08 | 惠州华阳医疗器械有限公司 | Antibacterial wound dressing and preparation method and application thereof |
| CN107307160A (en) * | 2017-06-29 | 2017-11-03 | 安徽康博特保健食品有限公司 | A kind of preparation method of shark chondroitin milk calcium pressed candy |
| CN107372992A (en) * | 2017-06-29 | 2017-11-24 | 安徽康博特保健食品有限公司 | A kind of preparation method of sealwort oyster pressed candy |
| CN108097314A (en) * | 2017-11-15 | 2018-06-01 | 昆明理工大学 | A kind of preparation method and application of dialdehyde cellulose SalenMX catalyst |
| CN110452509A (en) * | 2019-08-01 | 2019-11-15 | 山东省农业科学院农产品研究所 | One kind is fresh-keeping to use film |
| CN111663368A (en) * | 2020-06-16 | 2020-09-15 | 北京林业大学 | Preparation method of high-strength antibacterial coated paper |
| CN114149638A (en) * | 2021-12-15 | 2022-03-08 | 重庆会通科技有限公司 | Antibacterial ramie fiber reinforced polypropylene composite material and preparation method thereof |
| CN115785291A (en) * | 2023-01-19 | 2023-03-14 | 常熟威怡科技有限公司 | Preparation method and application of biguanide crosslinked carboxyl cellulose material |
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Cited By (19)
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| CN106280236A (en) * | 2016-08-26 | 2017-01-04 | 繁昌县倍思生产力促进中心有限公司 | A kind of wear-resistant antibacterial warming plate used for building exterior wall |
| CN106365584A (en) * | 2016-08-26 | 2017-02-01 | 繁昌县倍思生产力促进中心有限公司 | Preparation method of wear-proof insulation board for building external walls |
| CN106431102A (en) * | 2016-08-26 | 2017-02-22 | 繁昌县倍思生产力促进中心有限公司 | Phenolic foam heat-insulation board for external walls of buildings |
| CN106279858A (en) * | 2016-08-30 | 2017-01-04 | 安徽蓝德集团股份有限公司 | A kind of good coal mine cable protective cover material of antibacterial mechanical property |
| CN106317905A (en) * | 2016-08-30 | 2017-01-11 | 安徽蓝德集团股份有限公司 | Coal mine cable sheath material with excellent heat stability |
| CN107047992A (en) * | 2017-05-03 | 2017-08-18 | 丁永胜 | A kind of nutritious sheep feed |
| CN107087714A (en) * | 2017-05-03 | 2017-08-25 | 丁永胜 | A kind of high digestibility feed for sheep |
| CN107137749A (en) * | 2017-05-23 | 2017-09-08 | 惠州华阳医疗器械有限公司 | Antibacterial wound dressing and preparation method and application thereof |
| CN107307160A (en) * | 2017-06-29 | 2017-11-03 | 安徽康博特保健食品有限公司 | A kind of preparation method of shark chondroitin milk calcium pressed candy |
| CN107372992A (en) * | 2017-06-29 | 2017-11-24 | 安徽康博特保健食品有限公司 | A kind of preparation method of sealwort oyster pressed candy |
| CN108097314A (en) * | 2017-11-15 | 2018-06-01 | 昆明理工大学 | A kind of preparation method and application of dialdehyde cellulose SalenMX catalyst |
| CN108097314B (en) * | 2017-11-15 | 2020-11-17 | 昆明理工大学 | Preparation method and application of dialdehyde cellulose SalenMX catalyst |
| CN110452509A (en) * | 2019-08-01 | 2019-11-15 | 山东省农业科学院农产品研究所 | One kind is fresh-keeping to use film |
| CN110452509B (en) * | 2019-08-01 | 2021-09-07 | 山东省农业科学院农产品研究所 | Fresh-keeping film |
| CN111663368A (en) * | 2020-06-16 | 2020-09-15 | 北京林业大学 | Preparation method of high-strength antibacterial coated paper |
| CN111663368B (en) * | 2020-06-16 | 2022-06-28 | 北京林业大学 | Preparation method of high-strength antibacterial coated paper |
| CN114149638A (en) * | 2021-12-15 | 2022-03-08 | 重庆会通科技有限公司 | Antibacterial ramie fiber reinforced polypropylene composite material and preparation method thereof |
| CN115785291A (en) * | 2023-01-19 | 2023-03-14 | 常熟威怡科技有限公司 | Preparation method and application of biguanide crosslinked carboxyl cellulose material |
| CN115785291B (en) * | 2023-01-19 | 2023-05-09 | 常熟威怡科技有限公司 | Preparation method and application of biguanide crosslinked carboxyl cellulose material |
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Application publication date: 20140416 |