阅读说明：本技术 一种可低温加工的醋酸纤维素材料及其制备方法 (Cellulose acetate material capable of being processed at low temperature and preparation method thereof ) 是由 赵铭 台启龙 陈丽娟 于 2021-10-20 设计创作，主要内容包括：本发明公开了一种可低温加工的醋酸纤维素材料,按重量份计,原料组成包括：醋酸纤维素100份；增塑剂15～45份；改性剂0.1～2份；引发剂0.1～2份；其它助剂0.1～2份；所述改性剂选自缩水甘油醚类、异氰酸酯类、二酸酐类、丙烯酰胺类中的一种或多种。本发明公开了一种可低温加工的醋酸纤维素材料,利用增塑剂与特定改性剂的协同作用,可将醋酸纤维素材料的加工温度降低至120～160℃,不仅避免了加工过程中醋酸纤维素基材的分解,且大大降低了生产的能耗,更适合大规模工业化生产,制备得到的醋酸纤维素制品透明度高、颜色浅,且力学性能优异。(The invention discloses a low-temperature processable cellulose acetate material, which comprises the following raw materials in parts by weight: 100 parts of cellulose acetate; 15-45 parts of a plasticizer; 0.1-2 parts of a modifier; 0.1-2 parts of an initiator; 0.1-2 parts of other auxiliary agents; the modifier is selected from one or more of glycidyl ethers, isocyanates, diacid anhydrides and acrylamides. The invention discloses a cellulose acetate material capable of being processed at a low temperature, which can reduce the processing temperature of the cellulose acetate material to 120-160 ℃ by utilizing the synergistic effect of a plasticizer and a specific modifier, so that the decomposition of a cellulose acetate base material in the processing process is avoided, the energy consumption of production is greatly reduced, the cellulose acetate material is more suitable for large-scale industrial production, and the prepared cellulose acetate product has high transparency, light color and excellent mechanical property.)

1. A cellulose acetate material capable of being processed at low temperature is characterized by comprising the following raw materials in parts by weight:

the modifier is selected from one or more of glycidyl ethers, isocyanates, diacid anhydrides and acrylamides.

2. The cryogenically processable cellulose acetate material of claim 1, wherein the cellulose acetate is a cellulose diacetate derived from a cellulose acetate from wood pulp or bamboo pulp.

3. The cryogenically processable cellulose acetate material of claim 1, wherein the plasticizer is selected from one or more of the group consisting of triphenyl phosphate, triphenyl phosphite, polyethylene glycol, phthalates, triacetin, citrates.

4. The cryogenically processable cellulose acetate material of claim 1, wherein:

the glycidyl ether is selected from one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether and triethylene glycol diglycidyl ether;

the isocyanate is selected from one or more of triglycidyl isocyanurate, triallyl isocyanurate and tri-allylisocyanate;

the diacid anhydride is selected from one or more of succinic anhydride, glutaric anhydride, adipic anhydride and maleic anhydride;

the acrylamide is selected from N, N-methylene-bis-acrylamide.

5. The cryogenically processable cellulose acetate material of claim 1, wherein the initiator is selected from organic peroxide-based initiators and/or azo-based initiators.

6. The cryogenically processable cellulose acetate material of claim 1, wherein the other additives include antioxidants and/or lubricants.

7. The low temperature processable cellulose acetate material of any one of claims 1 to 6, wherein the raw material composition comprises, in weight percent:

8. the cryogenically processable cellulose acetate material of claim 7, wherein the modifying agent is selected from the group consisting of anhydrides and/or isocyanates.

9. The cryogenically processable cellulose acetate material of claim 8, wherein the raw material composition comprises, in weight percent:

10. a method of preparing the low temperature processable cellulose acetate material of any one of claims 1 to 9, comprising:

uniformly blending all the raw materials, and then performing extrusion, granulation and drying treatment to prepare the cellulose acetate material;

the extrusion temperature is 120-160 ℃;

or the following steps:

uniformly blending all the raw materials and then performing injection molding to prepare the cellulose acetate material;

the injection molding temperature is 120-160 ℃.

Technical Field

The invention belongs to the field of cellulose acetate materials, and particularly relates to a low-temperature processable cellulose acetate material and a preparation method thereof.

Background

Cellulose Acetate (CA) is a cellulose derivative obtained by acetylation of cellulose, and has been commercialized for the first time. The performance of the cellulose acetate depends on the acetylation degree of hydroxyl groups in the production process, and the cellulose acetate has the characteristics of good toughness, good luster, high mechanical strength, high transparency, stability to light, difficult combustion and the like. At present, cellulose acetate is widely used in the fields of cigarette filters, textile fibers, medical materials, separation membranes and the like.

However, the melting temperature of cellulose acetate is very close to the thermal decomposition temperature, so that the direct melting processing is difficult. At present, the solution casting method is generally adopted for processing and forming, but the method has high cost, and the used organic solvent has potential hazards (such as toxicity or flammability and the like), thereby bringing potential safety hazards to manufacturers and users.

At present, the research on cellulose acetate mainly focuses on improving the melt processing performance and the thermal stability, and the most common method is to pull the difference between the melting temperature and the thermal decomposition temperature of cellulose acetate by adding a plasticizer. However, the effect of lowering the melting temperature of cellulose acetate by only the plasticizer is limited. For example, chinese patent publication No. CN 108059734 a discloses an environment-friendly cellulose diacetate pellet and a preparation method thereof, and chinese patent publication No. CN 109503892A discloses a modified cellulose diacetate and a preparation method and use thereof. In the technical scheme, the phthalate, the glyceride and the citrate plasticizers are adopted, the temperature of the feeding section reaches 160 ℃, the temperature of the machine head reaches 230-240 ℃, and the cellulose acetate can be oxidized, degraded and the like at the processing temperature, so that the product is yellow and the mechanical property is reduced.

Disclosure of Invention

The invention discloses a cellulose acetate material capable of being processed at a low temperature, which can reduce the processing temperature of the cellulose acetate material to 120-160 ℃ by utilizing the synergistic effect of a plasticizer and a specific modifier, so that the decomposition of a cellulose acetate base material in the processing process is avoided, the energy consumption of production is greatly reduced, the cellulose acetate material is more suitable for large-scale industrial production, and the prepared cellulose acetate product has high transparency, light color and excellent mechanical property.

The specific technical scheme is as follows:

a cellulose acetate material capable of being processed at low temperature comprises the following raw materials in parts by weight:

the modifier is selected from one or more of glycidyl ethers, isocyanates, diacid anhydrides and acrylamides.

According to the formula of the cellulose acetate material disclosed by the invention, the processing temperature of the cellulose acetate material is reduced to 120-160 ℃ under the mutual synergistic action of the plasticizer and the specific modifier which are added into the cellulose acetate substrate at the same time.

Preferably, the cellulose acetate is cellulose diacetate, the source of which is selected from cellulose acetate from wood pulp or cellulose acetate from bamboo pulp, in view of raw material price and availability.

Preferably, the plasticizer is selected from one or more of triphenyl phosphate, triphenyl phosphite, polyethylene glycol, phthalate, glyceryl triacetate and citrate.

Preferably:

the glycidyl ether is selected from one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether and triethylene glycol diglycidyl ether;

the isocyanate is selected from one or more of triglycidyl isocyanurate, triallyl isocyanurate and tri-allylisocyanate;

the diacid anhydride is selected from one or more of succinic anhydride, glutaric anhydride, adipic anhydride and maleic anhydride;

the acrylamide is selected from N, N-methylene-bis-acrylamide.

Preferably, the initiator is selected from organic peroxide initiators and/or azo initiators.

Preferably, the other auxiliary agents include antioxidants and/or lubricants. The purpose of adding the antioxidant is to inhibit the degradation of cellulose acetate during processing; the purpose of adding the lubricant is to improve the fluidity of the melt and increase the surface gloss of the product.

Further preferably, the low-temperature processable cellulose acetate material comprises the following raw materials in parts by weight:

tests show that the specific formula has good continuity in the extrusion process, and the prepared cellulose acetate product has high transparency and basically has no yellowing or light yellow.

Still more preferably, the modifier is selected from the group consisting of anhydrides and/or isocyanates.

Tests show that after the types of the modifiers are further preferably the two types, the prepared cellulose acetate product is almost free from yellowing, high in transparency, colorless and better in mechanical property.

More preferably:

the cellulose acetate material capable of being processed at low temperature comprises the following raw materials in parts by weight:

the modifier is selected from the group consisting of anhydrides.

Tests show that the apparent property and the mechanical property of the prepared cellulose acetate product are both optimal under the condition of adopting the more preferable formula composition.

The invention also discloses a preparation method of the cellulose acetate material capable of being processed at low temperature, which comprises the following steps:

uniformly blending all the raw materials, and then performing extrusion, granulation and drying treatment to prepare the cellulose acetate material;

the extrusion temperature is 120-160 ℃;

or the following steps:

uniformly blending all the raw materials and then performing injection molding to prepare the cellulose acetate material;

the injection molding temperature is 120-160 ℃.

The cellulose acetate material disclosed by the invention can be formed by extrusion or injection molding, and the processing temperature can be controlled to be 120-160 ℃.

Preferably:

the raw material blending can be carried out in a high-speed mixer, the rotating speed is 500-1000 RPM, and the blending time is 30-60 min.

Preferably:

and during extrusion molding, the rotating speed of the screw is 50-300 rpm.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a cellulose acetate material capable of being processed at a low temperature, which can reduce the processing temperature of the cellulose acetate material to 120-160 ℃ by utilizing the synergistic effect of a plasticizer and a specific modifier, so that the decomposition of a cellulose acetate base material in the processing process is avoided, the energy consumption of production is greatly reduced, the cellulose acetate material is more suitable for large-scale industrial production, and the prepared cellulose acetate product has high transparency, light color and excellent mechanical property.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

100 parts of dried cellulose acetate (Wuhanpeng ramon Biotech Co., Ltd.), 0.5 part of modifier ethylene glycol diglycidyl ether (Adamas, RG), 0.2 part of initiator azobisisobutyronitrile (Adamas, RG), 30 parts of plasticizer triethyl citrate (Adamas, RG), 0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (Pasv, Irganox1076), 0.3 part of lubricant erucamide (Adamas, RG) are respectively weighed and added into a high-speed mixer, mixed at 800RPM for 30min, and then extruding and granulating on a screw extruder, wherein the temperature of a first zone is 120 ℃, the temperature of a second zone is 145 ℃, the temperature of a third zone is 145 ℃, the temperature of a fourth zone is 145 ℃, the temperature of a fifth zone is 145 ℃, the temperature of a sixth zone is 150 ℃, the temperature of a seventh zone is 150 ℃, the temperature of an eighth zone is 150 ℃, the temperature of a ninth zone is 150 ℃, and the temperature of a die head is 150 ℃, and the particles are dried to obtain the material. The material is suitable for extrusion and injection molding, and the molding temperature can be reduced to 120-160 ℃.

Example 2

The procedure is essentially the same as in example 1, except that the modifier ethylene glycol diglycidyl ether is replaced by maleic anhydride (Adamas, RG).

Example 3

The preparation process was essentially the same as in example 1, except that the modifier ethylene glycol diglycidyl ether was replaced with triglycidyl isocyanurate (Guangzhou macro Biotech Co., Ltd.).

Example 4

The procedure is essentially the same as in example 1, except that the modifier ethylene glycol diglycidyl ether is replaced by N, N-methylenebisacrylamide (Adamas, RG).

Example 5

Respectively weighing 100 parts of dried cellulose acetate (Wuhanpeng ramon Biotech Co., Ltd.), 1 part of modifier triglycidyl isocyanurate (Guangzhou macro-range Biotech Co., Ltd.), 0.3 part of initiator dicumyl peroxide (avadin, 99%), 25 parts of plasticizer glyceryl triacetate (Shandong Yousio chemical Co., Ltd.), 0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (basf, Irganox1076) and 0.3 part of lubricant erucamide (Adamas, RG) into a high-speed mixer, mixing at 800RPM for 30min, extruding and granulating on a screw extruder, wherein the temperature of a first zone is 120 ℃, the temperature of a second zone is 145 ℃, the temperature of a third zone is 145 ℃, the temperature of a fourth zone is 145 ℃, the temperature of a fifth zone is 145 ℃, the temperature of a sixth zone is 150 ℃, the temperature of a seventh zone is 150 ℃, the temperature of an eighth zone is 150 ℃, the temperature of a ninth zone is 150 ℃, the die head temperature is 150 ℃, and the particles are dried to obtain the material. The material is suitable for extrusion and injection molding, and the molding temperature can be reduced to 120-160 ℃.

Example 6

Respectively weighing 100 parts of dried cellulose acetate (Wuhanpeng ramon Biotech Co., Ltd.), 0.8 part of modifier succinic anhydride (Adamas, RG), 0.5 part of initiator benzoyl peroxide (Adamas, RG), 20 parts of plasticizer triphenyl phosphate (Adamas, RG), 0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (Pasf, Irganox1076) and 0.3 part of lubricant oleamide (Adamas, RG) into a high-speed mixer, mixing for 30min at 800RPM, and then extruding and granulating on a screw extruder, wherein the temperature of a first zone is 120 ℃, the temperature of a second zone is 145 ℃, the temperature of a third zone is 145 ℃, the temperature of a fourth zone is 145 ℃, the temperature of a fifth zone is 145 ℃, the temperature of a sixth zone is 150 ℃, the temperature of an eighth zone is 150 ℃, the temperature of a ninth zone is 150 ℃, and the particles are dried to obtain the material. The material is suitable for extrusion and injection molding, and the molding temperature can be reduced to 120-160 ℃.

Example 7

The preparation process was essentially the same as in example 1, except that the amount of triethyl citrate as the plasticizer in the raw material was replaced with 35 parts.

Comparative example 1

The preparation process is essentially the same as in example 1, except that no modifier and initiator are added to the raw material composition. And (3) extruding and granulating on a screw extruder, wherein when the extrusion temperature is lower than 160 ℃, the motor is overloaded due to insufficient melting of the materials, and the materials cannot be extruded. When the temperature is gradually increased to over 180 ℃, the extrusion granulation can be smoothly carried out. It is demonstrated that the addition of the plasticizer alone, without cross-linking graft modification of cellulose acetate, does not reduce the processing temperature of cellulose acetate to below 160 ℃.

Comparative example 2

The preparation process is essentially the same as in example 1, except that no plasticizer is added to the raw material composition. And (3) granulating on a screw extruder, wherein when the extrusion temperature is lower than 160 ℃, the motor is overloaded due to insufficient melting of the materials, and the materials cannot be extruded. When the temperature is gradually increased to more than 200 ℃, the extrusion granulation can be smoothly carried out. It is demonstrated that the processing temperature of cellulose acetate cannot be reduced to below 160 ℃ by performing crosslinking graft modification on cellulose acetate alone without adding a plasticizer.

By combining example 1, comparative example 1 and comparative example 2, it can be found that the synergistic effect of the crosslinking graft modification and the plasticizer is required to realize the processing and forming of the cellulose acetate at the temperature of below 160 ℃, and the effect of low-temperature processing cannot be achieved by carrying out the crosslinking graft modification or using the plasticizer alone.

The materials respectively prepared in the above groups of examples and comparative examples are subjected to injection molding to obtain standard sample bars, and the mechanical properties of the samples are respectively tested according to the methods specified in GB/T1040-92 plastic tensile property test method, GB/T9341-2008 plastic bending property determination and GB/T1043-2008 plastic simple beam impact property determination.

The process phenomena of the examples are shown in Table 1, and the mechanical property results are shown in Table 2.

TABLE 1

Numbering	Process phenomenon
		Example 1	The extrusion process has good continuity, the surfaces of the sample strips are smooth, the particles are transparent and light yellow
Example 2	Good continuity of the extrusion processThe sample strips had smooth surfaces, and the particles were very transparent and colorless
		Example 3	The extrusion process has good continuity, the surface of the sample strip is smooth, and the particles are transparent and colorless
Example 4	The extrusion process has good continuity, the surfaces of the sample strips are smooth, the particles are transparent and light yellow
		Example 5	The extrusion process has good continuity, the surface of a sample strip is smooth, and the particles are transparent and light yellow
Example 6	The extrusion process has good continuity, the surface of a sample strip is smooth, and the particles are transparent and light yellow
		Example 7	Good continuity of extrusion process, smooth surface of sample strip, transparent granules and light yellow
Comparative example 1	Uneven thickness of sample strip, easy breakage, opaque particles and deep yellow color
		Comparative example 2	Uneven thickness of sample strip, easy breakage, opaque particles and yellow brown

TABLE 2

The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.