CN102718986A - Lignin modified layered double hydroxide and preparation method thereof and rubber composite - Google Patents
Lignin modified layered double hydroxide and preparation method thereof and rubber composite Download PDFInfo
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- CN102718986A CN102718986A CN2012101411079A CN201210141107A CN102718986A CN 102718986 A CN102718986 A CN 102718986A CN 2012101411079 A CN2012101411079 A CN 2012101411079A CN 201210141107 A CN201210141107 A CN 201210141107A CN 102718986 A CN102718986 A CN 102718986A
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- compound
- ldh
- metal ion
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Abstract
The invention relates to a lignin compound modified LDH and a preparation method thereof and to a rubber composite comprising the lignin compound modified LDH. The lignin compound in-situ modifies LDH to obtain the lignin compound modified LDH which comprises, by mass, 10% to 70% of water. The mass ratio of the lignin compound to LDH is 1:2 to 1:10. The lignin compound modified LDH can be used as a reinforcing agent to be uniformly dispersed in a rubber matrix, and has the advantages of low cost and no pollution to the environment.
Description
Technical field
The present invention relates to field of compound material, relate in particular to compound-modified layered double-hydroxide of lignin and preparation method thereof, and with the rubber composite of the compound-modified layered double-hydroxide of this lignin as strengthening agent.
Background technology
Layered double-hydroxide (Layered double hydroxide, be called for short LDH) is claimed anionic clay or hydrotalcite-based compound again, its laminate by divalence (like Mg
2+) and trivalent (like Al
3+) the metal hydroxides composition, positively charged, interlayer have tradable negatively charged ion (like NO
3 -Or CO
3 2-) and the crystal water molecule.Magnalium type LDH was owing to both had Mg (OH)
2The initial decomposition temperature that when fire-retardant, has is high, caloric receptivity is big, press down the strong characteristics of cigarette ability, has Al (OH) again
3The promotion that when fire-retardant, has becomes charcoal, presses down the characteristics of cigarette, also has the characteristics that the laminate of polynite intercepts and receives extensive attention.If be applied to improve in polymeric matrix such as the rubber flame retardant properties of polymeric matrix.Yet the granularity of LDH is less; The surface has a large amount of activity hydroxies, in polymeric matrix, reunite easily, and LDH itself is kind of an inorganic materials; The interface compatibility of itself and most polymer materialss is poor; In polymeric matrix, be difficult for homodisperse, cause easily in the polymeric matrix that stress distribution is uneven, material physical property such as mechanical properties decrease if directly it is filled in.Therefore, be necessary before use LDH to be carried out organically-modified, improve the consistency of itself and polymeric matrix, make its homodisperse in polymeric matrix.
Summary of the invention
One embodiment of the invention provides compound-modified LDH of lignin and preparation method thereof, and the compound-modified LDH of this lignin is added into as loading material of rubber prepares rubber composite in the rubber matrix.
Among the compound-modified LDH of this lignin, by mass percentage, water cut is 10%～70%, and the mass ratio of lignin compound and LDH is 1:2～1:10.
The compound-modified LDH of this lignin can make according to the following steps: under room temperature condition, it is that mechanical stirring 1h makes lignin liquor in 5%～30% the sodium hydroxide solution that a certain amount of lignin compound is dissolved in weight concentration; Said lignin compound comprises at least a in alkali lignin, vitriol xylogen, sulfonated lignin or the methylolation xylogen; Preparation contains the mixed aqueous solution of divalent-metal ion and trivalent metal ion; Wherein divalent-metal ion and trivalent metal ion mol ratio are 1:1～4:1; The metals ion total concn is the mixed aqueous solution of 0.1～3 mol, and the mass ratio of metals ion and lignin compound is (12:1～3:5); Said divalent-metal ion can be Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, Pb
2+In a kind of, trivalent metal ion can be Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+In a kind of; In said lignin liquor, drip said metals ion mixed aqueous solution and mass concentration simultaneously and be 5%～30% alkaline solution, mechanical stirring and to keep the pH value be 7 ~ 13 drips off until metallic ion mixed liquor; Continue to stir 0.5～3h, be statically placed in crystallization 12～48h cold filtration in 50～90 ℃ the water-bath, with deionized water or distilled water wash solid, it is 10～70% lignin-modified LDH that drying obtains water cut.
The compound-modified LDH of this lignin can be used as strengthening agent to be added in the rubber, and the rubber mechanical property that not only can improve can also reduce Rubber processing modification cost.
In the rubber composite that one embodiment of the invention provides; The modification LDH of lignin compound that comprises rubber matrix and be dispersed in this rubber matrix wherein, presses mass ratio; In pure LDH, rubber matrix is 100 with the ratio that LDH modifies in this lignin compound: (10 ~ 30).
Compared with prior art, it is in-situ modified that the present technique scheme utilizes the lignin compound as AS LDH to be carried out, and solved pure LDH at the not good key technical problem of rubber matrix dispersiveness.This lignin compound can be obtained by biomass material, and the source is abundant, and is with low cost, simple with the technology of its modification LDH, and the modification LDH that makes can be dispersed in the rubber matrix, has overcome that traditional rubber reinforcing filler cost is high, the shortcoming of contaminate environment.
Description of drawings
A is the XRD synoptic diagram of the pure LDH of non-modified among Fig. 1, and b is the XRD synoptic diagram that sodium lignosulfonate is modified LDH (S-LDH);
A, b, c are respectively the sem photograph of NBR, 10LDH/NBR, 10S-LDH/NBR among Fig. 2.
Embodiment
In the compound-modified layered double-hydroxide of lignin provided by the invention, press mass ratio, water cut is 10%～70%, and lignin compound and LDH mass ratio are 1:2～1:10, and it can make according to the following steps:
Under step 1, the room temperature condition, it is that mechanical stirring 1h makes lignin liquor in 5%～30% the sodium hydroxide solution that the xylogen of certain mass is dissolved in weight concentration.
Said lignin compound comprises at least a in alkali lignin, vitriol xylogen, sulfonated lignin or the methylolation xylogen.Said alkaline solution can be sodium hydroxide solution or potassium hydroxide solution.
Step 2, preparation contain the mixed aqueous solution of divalent-metal ion and trivalent metal ion; Wherein divalent-metal ion and trivalent metal ion mol ratio are 4:1 ~ 1:1; The metals ion total concn is the mixed aqueous solution of 0.1～3 mol, and the mass ratio of metals ion and lignin compound is (12:1～3:5).
Divalent-metal ion in the said mixed aqueous solution is Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, or Pb
2+, trivalent metal ion is Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+In a kind of.
Step 3, in lignin liquor, to drip described hybrid metal solion and mass concentration simultaneously be 5%～30% alkaline solution, and mechanical stirring and to keep the pH value be 7～13 drips off until the hybrid metal solion, promptly obtains lignin-modified LDH.
Step 4, drip continued and stir 0.5～3h, be statically placed in crystallization 12～48h cold filtration in 50～90 ℃ the water-bath, with deionized water or distilled water wash solid, it is 10～70% lignin-modified LDH that drying obtains water cut.
To compound-modified layered double-hydroxide of lignin provided by the invention and preparation method thereof, and rubber composite is done more detailed explanation below in conjunction with specific embodiment and accompanying drawing.
Embodiment 1:
Prepare the magnesium nitrate of a certain amount of 0.50mol/L and the aluminum nitrate metallic ion mixed liquor of 0.25mol/L, Mg
2+With Al
3+Mol ratio be 1:1.It is in 17% the sodium hydroxide solution that the 2g alkali lignin is dissolved in the 200mL weight concentration, makes lignin liquor.At room temperature with churned mechanically condition under, with metallic ion mixed liquor be added drop-wise to lentamente in the lignin liquor to the pH value of solution value be 7, consume metallic ion mixed liquor 441g.Drip continued and stir 1h, behind 65 ℃ of water-bath crystallization 24h, throw out being filtered, wash, be dried to water cut is 50% lignin-modified LDH, and wherein the mass ratio of xylogen and LDH is about 1:10.By abovementioned steps, the consumption of adjustment xylogen makes the mass ratio of xylogen and LDH be respectively 3:10 and 1:2, obtains the lignin-modified LDH of different xylogen/LDH mass ratio, called after L-LDH.
With the L-LDH of the xylogen that obtains and LDH different mass ratio respectively with the blend in mill of styrene-butadiene rubber(SBR) matrix; Melting temperature is 80～100 ℃; To constant weight, three blocks of L-LDH/ styrene-butadiene rubber(SBR) rubber master batch, the mass ratio of L-LDH and styrene-butadiene rubber(SBR) is 30/100 in every block of said rubber rubber master batch.
Rubber ingredients such as zinc oxide, Triple Pressed Stearic Acid, accelerant CZ and sulphur are joined in the said styrene-butadiene rubber(SBR) rubber master batch by prescription shown in the table 1 successively, at room temperature mixing.After the mixing completion, the gained rubber unvulcanizate is vulcanized with vulcanizing press at 160 ℃, get lignin-modified LDH/ styrene-butadiene rubber composite material; Called after L-LDH/SBR; The matrix material of different xylogen/LDH mass ratio is designated as 3L-30LDH/SBR, 9L-30LDH/SBR, 15L-30LDH/SBR respectively.
Table 1 styrene-butadiene rubber(SBR) prescription
| Component | Massfraction |
| Styrene-butadiene rubber(SBR) | 100 |
| Zinc oxide | 5 |
| Triple Pressed Stearic Acid | 2 |
| Accelerant CZ | 1.5 |
| Sulphur | 2.5 |
Embodiment 2:
The preparation total amount is magnesium nitrate and the aluminum nitrate metallic ion mixed liquor of 0.25mol/L of the 0.75mol/L of 3000mL, Mg
2+With Al
3+Mol ratio be 4:1.Preparation 4000mL mass concentration is 5% sodium hydroxide solution.It is in 5% the sodium hydroxide solution that the 100g sodium lignosulfonate is dissolved in the 1000mL mass concentration, lignin liquor.Under room temperature and churned mechanically condition, said metallic ion mixed liquor and sodium hydroxide solution are added drop-wise in the said lignin liquor lentamente simultaneously and keep pH value of solution=9～13.Treat that metallic ion mixed liquor drips continued and stirs 1h, behind 65 ℃ of water-bath crystallization 24h, throw out being filtered, wash, be dried to water cut is 50% sodium lignosulfonate modification LDH, called after S-LDH, and wherein the massfraction of LDH is 70.5%.
With said S-LDH and paracril matrix by different mass ratioes, i.e. 10:100,20:100,30:100, blend in mill, melting temperature is 80～100 ℃, to constant weight, S-LDH/ paracril rubber master batch.
Rubber ingredients such as zinc oxide, Triple Pressed Stearic Acid, accelerant CZ and sulphur are joined in the above-mentioned paracril rubber master batch by prescription shown in the table 2 successively, at room temperature mixing.
Table 2 paracril prescription
| Component | Massfraction |
| Paracril | 100 |
| Zinc oxide | 5 |
| Triple Pressed Stearic Acid | 2 |
| Accelerant CZ | 1.5 |
| Sulphur | 2.5 |
The gained rubber unvulcanizate is vulcanized with vulcanizing press at 160 ℃, get lignin-modified LDH/ nitile-butadiene rubber composite material, called after S-LDH/NBR; Press the difference of S-LDH content; The gained rubber composite is designated as 10S-LDH/NBR, 20S-LDH/NBR, 30S-LDH/NBR respectively.
The comparative example 1:
At room temperature, add rubber ingredients such as zinc oxide, Triple Pressed Stearic Acid, accelerant CZ and sulphur to styrene-butadiene rubber(SBR) by the said prescription of table 1, even with mill mixing, vulcanize with vulcanizing press at 160 ℃ after rubber unvulcanizate placed 24h.
The comparative example 2:
At room temperature, pressing shown in the table 2 prescription and adding rubber ingredients such as zinc oxide, Triple Pressed Stearic Acid, accelerant CZ and sulphur to paracril, even with mill mixing, vulcanize with vulcanizing press at 160 ℃ after rubber unvulcanizate placed 24h.
The comparative example 3:
Prepare the magnesium nitrate of a certain amount of 0.50mol/L and the aluminum nitrate metallic ion mixed liquor of 0.25mol/L, Mg
2+With Al
3+Mol ratio be 1: 1.Preparation 200mL weight concentration is 17% sodium hydroxide solution.At room temperature with churned mechanically condition under, with metallic ion mixed liquor be added drop-wise to lentamente in the lignin liquor to the pH value of solution value be 7, consume metallic ion mixed liquor 441g.Drip continued and stir 1h, behind 65 ℃ of water-bath crystallization 24h, throw out being filtered, wash, be dried to water cut is 50% LDH.
With the pure LDH of synthetic and styrene-butadiene rubber(SBR) blend in mill, melting temperature is 80～100 ℃, to constant weight, gets LDH/ styrene-butadiene rubber(SBR) rubber master batch.
Rubber ingredients such as zinc oxide, Triple Pressed Stearic Acid, accelerant CZ and sulphur are joined in the said styrene-butadiene rubber(SBR) rubber master batch by prescription shown in the table 1 successively, at room temperature mixing.After the mixing completion, the gained rubber unvulcanizate is vulcanized with vulcanizing press at 160 ℃, get the LDH/ styrene-butadiene rubber composite material, called after 0L-30LDH/SBR.
The comparative example 4:
The preparation total amount is magnesium nitrate and the aluminum nitrate metallic ion mixed liquor of 0.25mol/L of the 0.75mol/L of 3000mL, Mg
2+With Al
3+Mol ratio be 4:1.Preparation 4000mL mass concentration is 5% sodium hydroxide solution, is designated as solution B.Preparation 1000mL mass concentration is 5% sodium hydroxide solution, is designated as solution C.It is in 5% the sodium hydroxide solution that the 100g sodium lignosulfonate is dissolved in the 1000mL mass concentration, lignin liquor.Under room temperature and churned mechanically condition, metallic ion mixed liquor and solution B are added drop-wise in solution C and the lignin liquor lentamente simultaneously and keep pH value of solution=9～11.Treat that metallic ion mixed liquor drips continued and stirs 1h, behind 65 ℃ of water-bath crystallization 24h, throw out being filtered, wash, be dried to water cut is 50% LDH.
Said LDH is pressed different mass ratio blend in mill with paracril, and melting temperature is 80～100 ℃, to constant weight, gets LDH/ paracril rubber master batch.
Rubber ingredients such as zinc oxide, Triple Pressed Stearic Acid, accelerant CZ and sulphur are joined in the above-mentioned paracril rubber master batch by prescription shown in the table 2 successively, at room temperature mixing.
The gained rubber unvulcanizate is vulcanized with vulcanizing press at 160 ℃, the LDH/ nitile-butadiene rubber composite material, called after LDH/NBR, different loading levels be designated as 10LDH/NBR, 20LDH/NBR, 30LDH/NBR respectively.
Referring to Fig. 1, a is the XRD figure of the pure LDH of non-modified, and b is the XRD figure that sodium lignosulfonate is modified LDH (S-LDH).Can know that from Fig. 1 compare with pure LDH, the diffraction peak position of S-LDH does not have considerable change; But the width at peak obviously increases and the intensity at peak obviously reduces; Show that sodium lignosulfonate can suppress the accumulation of LDH lamella, make that LDH particulate size is littler, also reduced the percent crystallinity of LDH simultaneously.
Referring to Fig. 2, a, b, c are respectively the sem photograph of NBR, 10LDH/NBR, 10S-LDH/NBR.Contrast b and c can know that it is more careful, even that S-LDH disperses in the NBR matrix, obviously be better than the dispersiveness of pure LDH in the NBR matrix, show to utilize the lignin compound that LDH is carried out in-situ modifiedly significantly improving the dispersiveness of LDH in rubber matrix.
Referring to table 3 and table 4, the mechanical property of lignin-modified LDH/ styrene-butadiene rubber composite material and lignin-modified LDH/ paracril is shown respectively.Can know that by this two table the lignin-modified LDH that the embodiment of the invention provides can obviously improve the mechanical property of rubber matrix.
The performance of the lignin-modified LDH/ styrene-butadiene rubber composite material of table 3
The performance of table 4 sulfonated lignin LDH/ nitile-butadiene rubber composite material
Claims (8)
1. compound-modified LDH of lignin, by mass percentage, water cut is 10%～70%, the mass ratio of lignin compound and LDH is 1:2～1:10.
2. the compound-modified LDH of lignin as claimed in claim 1 is characterized in that, said lignin compound is selected from least a in alkali lignin, vitriol xylogen, sulfonated lignin or the methylolation xylogen.
3. according to claim 1 or claim 2 the compound-modified LDH of lignin; It is characterized in that; The mol ratio of divalent-metal ion and trivalent metal ion is 1:1～4:1 among the compound-modified LDH of said lignin; The mass ratio of said divalent-metal ion and trivalent metal ion quality sum and lignin compound is 12:1～3:5, and said divalent-metal ion is Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, Pb
2+In a kind of, trivalent metal ion is Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+In a kind of.
4. the preparation method of the compound-modified LDH of lignin comprises: under room temperature condition, it is in 5%～30% the alkaline solution that the lignin compound is dissolved in weight concentration, makes lignin liquor; Preparation contains the mixed aqueous solution of divalent-metal ion and trivalent metal ion; Wherein divalent-metal ion and trivalent metal ion mol ratio are 1:1～4:1; The metals ion total concn is the mixed aqueous solution of 0.1～3 mol, and the mass ratio of metals ion and lignin compound is 12:1～3:5; In said lignin liquor, drip said metals ion mixed aqueous solution and said alkaline solution, stirring and keeping the pH value is 7 ~ 13, drips off until metallic ion mixed liquor; Stir 0.5～3h, be statically placed in crystallization 12～48h cold filtration in 50～90 ℃ the water-bath, washing, it is 10～70% lignin-modified LDH that drying obtains water cut.
5.. the preparation method of the compound-modified LDH of lignin as claimed in claim 4; It is characterized in that; Said lignin compound is selected from least a in alkali lignin, vitriol xylogen, sulfonated lignin or the methylolation xylogen, and said divalent-metal ion is Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, Pb
2+In a kind of, trivalent metal ion is Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+In a kind of.
6. rubber composite; Comprise rubber matrix and be dispersed in the compound-modified LDH of lignin in this rubber matrix that by mass ratio, the compound-modified LDH ratio of said rubber matrix and said lignin is 100: (10 ~ 30); Among the compound-modified LDH of said lignin; By mass percentage, water cut is 10%～70%, and the mass ratio of lignin compound and LDH is 1:2～1:10.
7. rubber composite as claimed in claim 6 is characterized in that, said lignin compound is selected from least a in alkali lignin, vitriol xylogen, sulfonated lignin or the methylolation xylogen.
8. like claim 6 or 7 described rubber composites; It is characterized in that; The mol ratio of divalent-metal ion and trivalent metal ion is 1:1～4:1 among the compound-modified LDH of said lignin; The mass ratio of said divalent-metal ion and trivalent metal ion quality sum and lignin compound is 12:1～3:5, and said divalent-metal ion is Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, Pb
2+In a kind of, trivalent metal ion is Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+In a kind of.
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| CN104371374A (en) * | 2014-10-15 | 2015-02-25 | 上海应用技术学院 | Method for surface modification of magnesium hydroxide flame retardant |
| CN106700579A (en) * | 2017-02-22 | 2017-05-24 | 武汉理工大学 | Lignin grafted magnesium aluminum-based layered double hydroxide modifier, anti-ultraviolet ageing asphalt and preparation method thereof |
| CN106800673A (en) * | 2017-02-22 | 2017-06-06 | 武汉理工大学 | Alkali lignin grafting magnesium-aluminum-based laminar double hydroxide modifying agent, ultraviolet aging resistance SBS modified pitch and preparation method thereof |
| CN106832973A (en) * | 2017-02-22 | 2017-06-13 | 武汉理工大学 | Sodium lignin sulfonate grafting magnesium-aluminum-based laminar double hydroxide modifying agent, ultraviolet aging resistance SBR modified pitch and preparation method thereof |
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| CN106800673B (en) * | 2017-02-22 | 2019-02-05 | 武汉理工大学 | Alkali lignin is grafted magnesium-aluminum-based laminar double hydroxide modifying agent, ultraviolet aging resistance SBS modified pitch and preparation method thereof |
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| CN114426685A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method for increasing particle size of lignin/styrene butadiene rubber composite particles |
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