CN111269542B - Preparation method of low-viscosity wood powder/polycaprolactone composite material - Google Patents

Preparation method of low-viscosity wood powder/polycaprolactone composite material Download PDF

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CN111269542B
CN111269542B CN202010262405.8A CN202010262405A CN111269542B CN 111269542 B CN111269542 B CN 111269542B CN 202010262405 A CN202010262405 A CN 202010262405A CN 111269542 B CN111269542 B CN 111269542B
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李春松
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Shanghai Ruiqi Plastic Industry Co ltd
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Abstract

A preparation method of low-viscosity wood flour/polycaprolactone composite material comprises the following steps: 1) Using ethylene-vinyl alcohol copolymer and lanthanum tris (2, 6-di-tert-butyl-4-methylphenoxy) (La (OAr) 3 ) As co-initiator to prepare high molecular weight polycaprolactone; 2) Dispersing the dried wood powder and maleic anhydride into pyridine, and reacting at 120 ℃ for 2h to prepare modified wood powder; 3) Heating the mixed solution of sodium hydroxide, sodium carbonate and sodium chloride to 60-75 ℃, injecting a calcium chloride solution in batches under rapid stirring, and reacting for 0.5h to obtain calcium carbonate nanorods; 4) Adding sodium laurate hot ethanol solution, and carrying out reflux reaction; 5) Preparing a composite material: premixing the modified calcium carbonate nano-rods, the modified wood powder and the polycaprolactone, and banburying to obtain a blending product; 6) And (3) performing compression molding to obtain the low-viscosity wood powder/polycaprolactone composite material. The method enables the wood powder and the inorganic particles to be uniformly dispersed in the polycaprolactone, improves the mechanical properties such as tensile strength and the like, and reduces the melt viscosity.

Description

Preparation method of low-viscosity wood powder/polycaprolactone composite material
Technical Field
The invention relates to a low-viscosity polymer composite material and a preparation method thereof, in particular to a preparation method of low-viscosity wood powder/polycaprolactone composite material.
Background
Polycaprolactone, also known as polyepsilon caprolactone, has the advantages of good thermal stability, large elongation at break, good toughness and degradability, and can be completely degraded into water and carbon dioxide in water and soil, so that attention is paid. However, polycaprolactone has the disadvantages of low modulus, low melting point and high price, so that the large-scale development of polycaprolactone is limited. In recent years, degradable natural materials (such as starch, wood flour and the like) are introduced into degradable polymers so as to reduce the cost of the degradable materials, and natural materials or inorganic micro-nano materials are introduced into the polymers so as to improve the mechanical properties of the polymers. However, since natural materials such as starch and inorganic micro-nano materials have hydrophilicity, and the interface bonding force between the starch and polymers is weak, the compatibility is generally poor, so that the mechanical property of the composite material is rather reduced, and especially when the starch content is relatively high (for example, more than 40%), the phenomenon is further aggravated, and the mechanical property of the composite material is greatly reduced. How to uniformly disperse the natural material and polycaprolactone and still maintain or even improve the mechanical properties when a large amount of cheap natural material is used is still a problem to be solved. And because the inorganic particles are not easy to deform and flow, the internal friction force in the composite material is greatly increased, which is reflected by the increase of melt viscosity and is difficult to process. How to uniformly disperse inorganic particles in polycaprolactone and reduce melt viscosity while improving mechanical properties such as tensile strength of the polycaprolactone is still a problem to be solved.
Disclosure of Invention
The invention relates to a preparation method of low-viscosity wood powder/polycaprolactone composite material, aiming at solving the technical problem of improving the compatibility of wood powder, inorganic nano particles and high-molecular-weight polycaprolactone, uniformly dispersing the wood powder and the inorganic particles in the polycaprolactone, improving the mechanical properties such as tensile strength and the like and simultaneously reducing the melt viscosity.
A preparation method of low-viscosity wood flour/polycaprolactone composite material comprises the following steps:
1) Preparing polycaprolactone: introducing nitrogen after the reactor is vacuumized, adding ethylene-vinyl alcohol copolymer, adding dried epsilon-caprolactone into the reactor, heating in oil bath to 160-180 ℃ for melting for 1h, cooling to 110-130 ℃ after the ethylene-vinyl alcohol copolymer is dissolved in the epsilon-caprolactone, adding tris (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum (La (OAr) 3 ) Reacting an initiator at constant temperature for 15-20h, dissolving the product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: heating a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride to 60-75 ℃, injecting a calcium chloride solution in batches under rapid stirring, continuously stirring and reacting for 0.5h after the feeding is finished, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
4) Modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60-75 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a hot ethanol solution of sodium laurate, carrying out reflux reaction for 2-3h at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
5) Preparing a composite material: premixing the modified calcium carbonate nanorods and the modified wood flour obtained in the step 4) with polycaprolactone, and banburying in a banbury mixer for 15min at 90 ℃ to obtain a blending product;
6) And (3) pressing and forming the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
In the step 3), the concentration of the sodium hydroxide, the concentration of the sodium chloride and the concentration of the sodium carbonate in the mixed solution of the sodium hydroxide, the sodium carbonate and the sodium chloride are respectively 0.2mol/L, 0.3mol/L and 0.15mol/L.
In the step 3), the concentration of the calcium chloride solution is 0.15mol/L, 5mL is added each time, the time interval is 5-8s, and the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.7-0.9.
The mass ratio of the wood powder to the polycaprolactone is about 0.3-0.5: 1.
In the step 4), the mass ratio of the calcium carbonate nano-rods to the sodium laurate is 1: 0.1-0.3.
In the step 5), the mass ratio of the modified calcium carbonate nano-rod to the polycaprolactone is 0.1-0.2: 1.
The mass ratio of the initiator to the monomer is 1: 10, and the mass ratio of the ethylene-vinyl alcohol copolymer to the tris (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum is 1: 0.3.
The ethylene content of the ethylene-vinyl alcohol copolymer was 30%.
Advantageous effects
The invention adopts ethylene-vinyl alcohol copolymer and lanthanum tris (2, 6-di-tert-butyl-4-methylphenoxy) (La (OAr) 3 ) As a coinitiator, the preparation of which has a molecular weight of up to 10 5 The polycaprolactone of (1).
The calcium carbonate nanorods are modified by using the sodium laurate, so that the calcium carbonate nanorods are changed from hydrophilicity to hydrophobicity, and the compatibility of the calcium carbonate nanorods with polycaprolactone is improved. By controlling the reaction parameters of the nanorod preparation process, the length of the nanorod is controlled to be 600-900nm, and the phenomena of self winding, agglomeration and the like caused by the overlong length of the calcium carbonate one-dimensional structure are avoided, so that the dispersion of the calcium carbonate in polycaprolactone is not facilitated. In a molten state, polymer molecular chains can flow relatively, the material has certain viscosity due to the fact that longer molecular chains are curled and wound, after calcium carbonate nanorods are added, the nanorods with one-dimensional structures can be arranged in a certain orientation mode at a low shear rate, winding among the high molecular chains is hindered, even if a large amount of wood powder is introduced, the lower viscosity can be still kept, and processing of the composite material is facilitated.
In the preparation process of the calcium carbonate, the concentration of sodium hydroxide and sodium carbonate is controlled, the pH value of a reaction system is controlled, the initial nucleation rate and the later anisotropic growth of the calcium carbonate are controlled by the concentration of sodium chloride and the feeding speed of calcium chloride, and the nano rod with uniform size and good dispersibility is finally obtained.
Detailed Description
The tensile strength of the composite was measured using GB/T1040-92 at a test speed of 2mm/min and a sample size of 250mm 25mm 3mm.
Example 1
1) Preparing polycaprolactone: vacuumizing the reactor, introducing nitrogen, adding ethylene-vinyl alcohol copolymer with ethylene content of 30%, adding dried epsilon-caprolactone into the reactor, heating in oil bath to 160 deg.C for 1h, cooling to 110 deg.C after ethylene-vinyl alcohol copolymer is dissolved in epsilon-caprolactone, and adding lanthanum tris (2, 6-di-tert-butyl-4-methylphenoxy) (La (OAr) 3 ) Initiator with the mass ratio of 1: 10 to monomer, ethylene-vinyl alcohol copolymer with the mass ratio of 1: 0.3 to tris (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum, reacting for 15h at constant temperature, dissolving the product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone with the molecular weight of 1.8 x 10 5 The viscosity measured by an Ubbelohde viscometer is 0.74dL/g;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) heating a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride to 60 ℃, injecting a calcium chloride solution in batches with the concentration of 0.2mol/L, the concentration of 0.3mol/L and the concentration of 0.15mol/L, adding 5mL each time at 5-8s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.9, continuously stirring and reacting for 0.5h after the addition is finished, filtering, washing with deionized water to obtain calcium carbonate nanorods;
4) Modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, carrying out reflux reaction on calcium carbonate nanorods and sodium laurate at a mass ratio of 1: 0.2 at 80 ℃ for 3 hours, cooling, filtering, washing with hot ethanol, and drying;
5) Preparing a composite material: premixing the modified calcium carbonate nanorods, the modified wood powder and the polycaprolactone obtained in the step 4), wherein the mass ratio of the modified calcium carbonate nanorods, the wood powder and the polycaprolactone is 0.1: 0.5: 1, and banburying in an internal mixer at 90 ℃ for 15min to obtain a blended product;
6) And (3) pressing and forming the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
The composite material has tensile strength of 15.4MPa and viscosity of 0.61dL/g measured with an Ubbelohde viscometer.
Example 2
1) Preparing polycaprolactone: vacuumizing the reactor, introducing nitrogen, adding ethylene-vinyl alcohol copolymer with ethylene content of 30%, adding dried epsilon-caprolactone into the reactor, heating in oil bath to 160 deg.C to melt for 1h, cooling to 110 deg.C after the ethylene-vinyl alcohol copolymer is dissolved in epsilon-caprolactone, adding lanthanum tris (La (OAr) 2, 6-di-tert-butyl-4-methylphenoxy) 3 ) Initiator with the mass ratio of 1: 10 to monomer, ethylene-vinyl alcohol copolymer with the mass ratio of 1: 0.3 to tris (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum, reacting for 15h at constant temperature, dissolving the product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone with the molecular weight of 1.8 x 10 5 The viscosity measured by an Ubbelohde viscometer is 0.74dL/g;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) heating a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride to 60 ℃, injecting a calcium chloride solution in batches with the concentration of 0.2mol/L, the concentration of 0.3mol/L and the concentration of 0.15mol/L, adding 5mL each time at 5-8s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.7, continuously stirring and reacting for 0.5h after the addition is finished, filtering, washing with deionized water to obtain calcium carbonate nanorods;
4) Modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, performing reflux reaction at 80 ℃ for 3 hours, cooling, filtering, washing with hot ethanol, and drying, wherein the mass ratio of calcium carbonate nanorods to sodium laurate is 1: 0.3;
5) Preparing a composite material: premixing the modified calcium carbonate nanorods, the modified wood flour and polycaprolactone obtained in the step 4), wherein the mass ratio of the modified calcium carbonate nanorods, the wood flour and the polycaprolactone is 0.2: 0.5: 1, and banburying in a banbury mixer at 90 ℃ for 15min to obtain a blended product;
6) And (3) pressing and forming the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
The test shows that the tensile strength of the composite material is 16.1MPa, and the viscosity of the composite material is 0.64dL/g measured by a black-type viscometer.
Example 3
1) Preparing polycaprolactone: vacuumizing the reactor, introducing nitrogen, adding ethylene-vinyl alcohol copolymer with ethylene content of 30%, adding dried epsilon-caprolactone into the reactor, heating in oil bath to 160 ℃ to melt for 1h, cooling after the ethylene-vinyl alcohol copolymer is dissolved in the epsilon-caprolactoneAdding a tri (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum (La (OAr) 3) initiator at 110 ℃, wherein the mass ratio of the initiator to the monomer is 1: 10, the mass ratio of the ethylene-vinyl alcohol copolymer to the tri (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum is 1: 0.3, reacting at constant temperature for 15 hours, dissolving a product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone with the molecular weight of 1.8 x 10 5 The viscosity measured by an Ubbelohde viscometer is 0.74dL/g;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium chloride solution in batches with the concentration of 0.2mol/L, the concentration of 0.3mol/L and the concentration of 0.15mol/L in a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride, heating to 60 ℃, rapidly stirring, adding 5mL of the calcium chloride solution each time at 5-8s intervals, wherein the molar ratio of sodium carbonate to calcium chloride is 1: 0.9 in the reaction process, continuously stirring for reaction for 0.5h after the addition is finished, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
4) Modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, carrying out reflux reaction on calcium carbonate nanorods and sodium laurate at a mass ratio of 1: 0.2 at 80 ℃ for 3 hours, cooling, filtering, washing with hot ethanol, and drying;
5) Preparing a composite material: premixing the modified calcium carbonate nanorods, the modified wood powder and the polycaprolactone obtained in the step 4), wherein the mass ratio of the modified calcium carbonate nanorods, the wood powder and the polycaprolactone is 0.1: 0.2: 1, and banburying in an internal mixer at 90 ℃ for 15min to obtain a blended product;
6) And (3) pressing and forming the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
The test shows that the tensile strength of the composite material is 5.1MPa, and the viscosity of the composite material is 0.26dL/g measured by a black-type viscometer.
Example 4
1) Preparing polycaprolactone: vacuumizing the reactor, introducing nitrogen, adding ethylene-vinyl alcohol copolymer with ethylene content of 30%, adding dried epsilon-caprolactone into the reactor, heating in oil bath to 160 deg.C to melt for 1h, cooling to 110 deg.C after the ethylene-vinyl alcohol copolymer is dissolved in epsilon-caprolactone, adding lanthanum tris (La (OAr) 2, 6-di-tert-butyl-4-methylphenoxy) 3 ) Initiator with the mass ratio of 1: 10 to monomer, ethylene-vinyl alcohol copolymer with the mass ratio of 1: 0.3 to tris (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum, reacting for 15h at constant temperature, dissolving the product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone with the molecular weight of 1.8 x 10 5 The viscosity measured by an Ubbelohde viscometer is 0.74dL/g;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing a composite material: premixing modified wood powder and polycaprolactone, wherein the mass ratio of the modified calcium carbonate nanorods to the wood powder to the polycaprolactone is 0.5: 1, and banburying in an internal mixer at 90 ℃ for 15min to obtain a blending product;
4) And (3) pressing and forming the blended product obtained in the step 3) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
The test shows that the tensile strength of the composite material is 7.9MPa, and the viscosity of the composite material is 0.89dL/g measured by a black-type viscometer.
Example 5
1) Preparing polycaprolactone: vacuumizing the reactor, introducing nitrogen, adding an ethylene-vinyl alcohol copolymer with the ethylene content of 30%, adding dried epsilon-caprolactone into the reactor, heating the mixture in an oil bath to 160 ℃ for melting for 1h, cooling the mixture to 110 ℃ after the ethylene-vinyl alcohol copolymer is dissolved in the epsilon-caprolactone, adding a tri (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum (La (OAr) 3) initiator, wherein the mass ratio of the initiator to the monomer is 1: 10, and the mass ratio of the ethylene-vinyl alcohol copolymer to the tri (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum is 1: 0.3 and is constantReacting at room temperature for 15h, dissolving the product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone with molecular weight of 1.8 × 10 5 The viscosity measured by an Ubbelohde viscometer is 0.74dL/g;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) heating a mixed solution of sodium hydroxide, sodium carbonate and sodium nitrate to 60 ℃, wherein the concentration of the sodium hydroxide is 0.2mol/L, the concentration of the sodium nitrate is 0.3mol/L, the concentration of the sodium carbonate is 0.15mol/L, heating to 60 ℃, injecting a calcium nitrate solution in batches under rapid stirring, the concentration of the calcium nitrate solution is 0.15mol/L, adding 5mL each time for 5-8s, the time interval is 1-8 s, the molar ratio of the sodium carbonate to the calcium nitrate in the reaction process is 1: 0.9, continuously stirring for reacting for 0.5h after the addition is finished, filtering, and washing with deionized water to obtain calcium carbonate nanorods with nonuniform shapes and sizes;
4) Modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, carrying out reflux reaction on calcium carbonate nanorods and sodium laurate at a mass ratio of 1: 0.2 at 80 ℃ for 3 hours, cooling, filtering, washing with hot ethanol, and drying;
5) Preparing a composite material: premixing the modified calcium carbonate nanorods, the modified wood flour and polycaprolactone obtained in the step 4), wherein the mass ratio of the modified calcium carbonate nanorods, the wood flour and the polycaprolactone is 0.1: 0.5: 1, and banburying in a banbury mixer at 90 ℃ for 15min to obtain a blended product;
6) And (3) pressing and forming the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
The test shows that the tensile strength of the composite material is 9.2MPa, and the viscosity of the composite material is 0.79dL/g measured by an Ubbelohde viscometer.
Example 6
1) Preparing polycaprolactone: introducing nitrogen after the reactor is vacuumized, adding ethylene-vinyl alcohol copolymer with 30 percent of ethylene content,adding dried epsilon-caprolactone into a reactor, heating in an oil bath to 160 ℃ for melting for 1h, cooling to 110 ℃ after ethylene-vinyl alcohol copolymer is dissolved in the epsilon-caprolactone, and adding lanthanum tris (2, 6-di-tert-butyl-4-methylphenoxy) (La (OAr) 3 ) Initiator with the mass ratio of 1: 10 to monomer, ethylene-vinyl alcohol copolymer with the mass ratio of 1: 0.3 to tris (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum, reacting for 15h at constant temperature, dissolving the product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone with the molecular weight of 1.8 x 10 5 The viscosity measured by an Ubbelohde viscometer is 0.74dL/g;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium chloride solution in batches under the conditions that the concentration of sodium hydroxide in a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride is 0.2mol/L, the concentration of sodium chloride is 0.1mol/L and the concentration of sodium carbonate is 0.15mol/L, heating to 60 ℃, rapidly stirring, adding 5mL of the calcium chloride solution each time at 5-8s intervals, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.9, continuously stirring for reacting for 0.5h after the addition is finished, filtering, and washing with deionized water to obtain calcium carbonate nanospheres and nanorods;
4) Modification of calcium carbonate: adding ethanol into a reaction kettle, heating to 60 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, wherein the mass ratio of the calcium carbonate to the sodium laurate is 1: 0.2, carrying out reflux reaction at 80 ℃ for 3 hours, cooling, filtering, washing with hot ethanol, and drying;
5) Preparing a composite material: premixing the modified calcium carbonate, the modified wood flour and the polycaprolactone obtained in the step 4), wherein the mass ratio of the modified calcium carbonate nanorods, the wood flour and the polycaprolactone is 0.1: 0.5: 1, and banburying in a banbury mixer at 90 ℃ for 15min to obtain a blended product;
6) And (3) pressing and forming the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
The test shows that the tensile strength of the composite material is 6.9MPa, and the viscosity of the composite material is 0.80dL/g measured by a black-type viscometer.
Example 7
1) Preparing polycaprolactone: vacuumizing a reactor, introducing nitrogen, adding an ethylene-vinyl alcohol copolymer with the ethylene content of 30%, adding dried epsilon-caprolactone into the reactor, heating the mixture in an oil bath to 160 ℃ for melting for 1h, cooling the mixture to 110 ℃ after the ethylene-vinyl alcohol copolymer is dissolved in the epsilon-caprolactone, adding a tri (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum (La (OAr) 3) initiator, wherein the mass ratio of the initiator to a monomer is 1: 10, the mass ratio of the ethylene-vinyl alcohol copolymer to the tri (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum is 1: 0.3, reacting for 15h at a constant temperature, dissolving a product with chloroform, adding heptane for precipitation, and drying to obtain polycaprolactone with the molecular weight of 1.8 x 105, wherein the viscosity is 0.74dL/g measured by an UK viscometer;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: the method comprises the following steps of (1) injecting a calcium chloride solution in batches under the conditions that the concentration of sodium hydroxide in a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride is 0.2mol/L, the concentration of sodium chloride is 0.3mol/L and the concentration of sodium carbonate is 0.15mol/L, heating to 60 ℃, rapidly stirring, adding 3mL of the calcium chloride solution each time at 5-8s, the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.9, continuously stirring for reaction for 0.5h after the addition is finished, filtering, and washing with deionized water to obtain calcium carbonate nanospheres;
4) Modification of calcium carbonate: adding ethanol into a reaction kettle, heating to 60 ℃, adding the calcium carbonate obtained in the step 1) into the reaction kettle, uniformly stirring, adding a sodium laurate hot ethanol solution, wherein the mass ratio of the calcium carbonate to the sodium laurate is 1: 0.2, carrying out reflux reaction at 80 ℃ for 3 hours, cooling, filtering, washing with hot ethanol, and drying;
5) Preparing a composite material: premixing the modified calcium carbonate, the modified wood flour and the polycaprolactone obtained in the step 4), wherein the mass ratio of the modified calcium carbonate nanorods, the wood flour and the polycaprolactone is 0.1: 0.5: 1, and banburying in a banbury mixer at 90 ℃ for 15min to obtain a blended product;
6) And (3) pressing and forming the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material.
The test shows that the tensile strength of the composite material is 6.2MPa, and the viscosity of the composite material is 0.82dL/g measured by an Ubbelohde viscometer.

Claims (2)

1. A preparation method of low-viscosity wood powder/polycaprolactone composite material is characterized by comprising the following steps: the method comprises the following steps:
1) Preparing polycaprolactone: introducing nitrogen after the reactor is vacuumized, adding ethylene-vinyl alcohol copolymer, adding dried epsilon-caprolactone into the reactor, heating the mixture in an oil bath to 160-180 ℃ to melt the mixture for 1h, cooling the mixture to 110-130 ℃ after the ethylene-vinyl alcohol copolymer is dissolved in the epsilon-caprolactone, adding a tri (2, 6-di-tert-butyl-4-methylphenoxy) lanthanum (La (OAr) 3) initiator, reacting the mixture at constant temperature for 15-20h, dissolving a product with chloroform, adding heptane for precipitation, and drying the precipitate to obtain polycaprolactone;
2) Wood powder modification: weighing wood flour, drying in vacuum at 80 ℃ to constant weight, weighing maleic anhydride, dispersing the dried wood flour and maleic anhydride into pyridine, reacting for 2h at 120 ℃, filtering, washing and drying to obtain modified wood flour;
3) Preparing calcium carbonate nanorods: heating a mixed solution of sodium hydroxide, sodium carbonate and sodium chloride to 60-75 ℃, injecting a calcium chloride solution in batches under rapid stirring, continuously stirring and reacting for 0.5h after the feeding is finished, filtering, and washing with deionized water to obtain calcium carbonate nanorods;
4) Modification of calcium carbonate nanorods: adding ethanol into a reaction kettle, heating to 60-75 ℃, adding the calcium carbonate obtained in the step 3) into the reaction kettle, uniformly stirring, adding a hot ethanol solution of sodium laurate, carrying out reflux reaction for 2-3h at 80 ℃, cooling, filtering, washing with hot ethanol, and drying;
5) Preparing a composite material: premixing the modified calcium carbonate nanorods, the modified wood powder and the polycaprolactone obtained in the step 4), and banburying in an internal mixer at 90 ℃ for 15min to obtain a blending product;
6) Pressing and molding the blended product obtained in the step 5) at 90 ℃ to obtain the low-viscosity wood powder/polycaprolactone composite material;
in the step 3), the concentration of sodium hydroxide in the mixed solution of sodium hydroxide, sodium carbonate and sodium chloride is 0.2mol/L, the concentration of sodium chloride is 0.3mol/L, and the concentration of sodium carbonate is 0.15mol/L;
in the step 3), the concentration of the calcium chloride solution is O.15mol/L, 5mL is added each time, the time interval is 5-8s, and the molar ratio of sodium carbonate to calcium chloride in the reaction process is 1: 0.7-0.9;
in the step 4), the mass ratio of the calcium carbonate nano-rods to the sodium laurate is 1: 0.1-0.3;
in the step 5), the mass ratio of the modified calcium carbonate nano-rod to the polycaprolactone is 0.1-0.2: 1.
2. The method of claim 1, wherein: the mass ratio of the wood powder to the polycaprolactone is 0.3-0.5: 1.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1367188A (en) * 2002-02-10 2002-09-04 复旦大学 Method for preparing macromolecular weight branched polycaprolactone
CN102952385A (en) * 2012-10-29 2013-03-06 暨南大学 Modified halloysite nanotube / biodegradable polyester composite material and preparation method thereof
CN103059274A (en) * 2013-01-07 2013-04-24 四川大学 Aliphatic polyester/calcium carbonate composite material and its preparation method
CN105802145A (en) * 2016-03-30 2016-07-27 亿帆鑫富药业股份有限公司 Biodegradable thermoplastic elastomer and production method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1367188A (en) * 2002-02-10 2002-09-04 复旦大学 Method for preparing macromolecular weight branched polycaprolactone
CN102952385A (en) * 2012-10-29 2013-03-06 暨南大学 Modified halloysite nanotube / biodegradable polyester composite material and preparation method thereof
CN103059274A (en) * 2013-01-07 2013-04-24 四川大学 Aliphatic polyester/calcium carbonate composite material and its preparation method
CN105802145A (en) * 2016-03-30 2016-07-27 亿帆鑫富药业股份有限公司 Biodegradable thermoplastic elastomer and production method thereof

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