CN114521673A - Composite plasticizer and preparation method and application thereof - Google Patents
Composite plasticizer and preparation method and application thereof Download PDFInfo
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- CN114521673A CN114521673A CN202210191313.4A CN202210191313A CN114521673A CN 114521673 A CN114521673 A CN 114521673A CN 202210191313 A CN202210191313 A CN 202210191313A CN 114521673 A CN114521673 A CN 114521673A
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims abstract description 77
- 235000013773 glyceryl triacetate Nutrition 0.000 claims abstract description 36
- 229960002622 triacetin Drugs 0.000 claims abstract description 36
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 150000002989 phenols Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 6
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 33
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 33
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- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
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- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 14
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000001920 pimenta acris kostel leaf oil terpeneless Substances 0.000 claims description 8
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- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 7
- 239000001069 triethyl citrate Substances 0.000 claims description 7
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000013769 triethyl citrate Nutrition 0.000 claims description 7
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 claims description 5
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- 239000005770 Eugenol Substances 0.000 description 4
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- 230000000840 anti-viral effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000002213 flavones Chemical class 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 150000002216 flavonol derivatives Chemical class 0.000 description 1
- 235000011957 flavonols Nutrition 0.000 description 1
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- 239000001087 glyceryl triacetate Substances 0.000 description 1
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- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
- A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
Abstract
The invention discloses a composite plasticizer and a preparation method and application thereof, wherein the composite plasticizer is prepared from the following raw materials in parts by weight: 16-90 parts of compound master batch, 13-40 parts of glycerol triacetate, 5-10 parts of phenol derivatives and 13-40 parts of auxiliaries, wherein the compound master batch comprises at least two of polyol plasticizers, o-benzene plasticizers and citrate micromolecule plasticizers. The composite plasticizer is compounded by using a polyol plasticizer, an o-benzene plasticizer and a citrate micromolecule plasticizer as a master batch, so that the curing time and the curing rate of the plasticizer can be greatly improved. And the phenol derivatives and the auxiliary agents are added into the master batch, so that the adsorbability of the filter rod can be effectively improved, and the physical health of a smoker is facilitated. Therefore, the plasticizer can effectively reduce harmful ingredients in cigarette smoke, can reduce the production cost of the filter rod, improves the curing efficiency and has higher economic benefit.
Description
Technical Field
The invention relates to the technical field of cigarette filter tip materials, in particular to a composite plasticizer and a preparation method and application thereof.
Background
With the development of the tobacco industry, in order to meet the health concept demand of consumers, various types of cigarette products, such as slim cigarettes, ultrafine cigarettes, traditional electronic cigarettes, low-temperature non-combustible cigarettes and the like, are introduced on the market. The filter rod is an indispensable part of cigarettes, and the value of the filter rod in cigarette products is increasingly important. The common cigarette filter rod material is generally selected from cellulose acetate. Cellulose acetate is an environment-friendly material with biodegradability, is derived from cellulose in a plant body, has good transparency and mechanical properties, and is also a cellulose derivative which is most widely applied at present. However, a large number of phthalidyl and hydroxyl groups are distributed in the molecular chain of the cellulose acetate, and the phthalidyl and the hydroxyl groups belong to polar molecules, and the polar groups make the molecular chain of the cellulose acetate rigid, and strong interaction force exists among the molecules, so that the molecular chain segment is weak in flexibility and difficult to process. Without improvement, cellulose acetate is difficult to maintain without degradation above the melting point, limiting its use and spread.
At present, in order to meet the requirement of cigarette processing performance, a plasticizer is required to be used or a cellulose acetate molecular chain is required to be modified in the process of forming a filter stick from an acetate fiber tow. The plasticizing modification method is simple, can utilize the advantages of the original substances and avoid the disadvantages of the original substances, and is a common modification means for cellulose in high polymer materials. In the prior art, a plasticizer commonly used for the cigarette acetate fiber filter stick is glycerol triacetate commonly known as triglyceride and is colorless viscous liquid, but the glycerol triacetate serving as a slow-drying plasticizer has low plasticizing efficiency and poor plasticizing effect and cannot meet the diversified requirements of the existing tobacco.
For example, the application number is [ CN201811452534.2 ] the cigarette filter stick composite plasticizer and the application thereof are characterized in that tri-n-butyl citrate (TBC), triethyl citrate (TEC) and triacetyl Glycerine (GT) are compounded, and the aim of adjusting or partially enhancing the hardness and the related mechanical properties of the cigarette filter stick can be fulfilled by changing the proportion of different components. The composite plasticizer is based on the preparation process of the traditional filter stick, and can improve various mechanical properties of the filter stick on the premise of ensuring the conventional requirements of the filter stick such as suction resistance and the like by adjusting the proportion of different raw materials in a plasticizer system and assisting in temperature and pressure adjustment.
However, the above plasticizer has a long curing time and a low curing efficiency, and when the amount of the plasticizer is large, the absorption and deterioration ability of cellulose acetate itself is also affected.
Disclosure of Invention
In order to solve the problems, the invention provides a composite plasticizer and a preparation method and application thereof. And the phenol derivatives and the auxiliary agents are added into the master batch, so that the adsorbability of the filter rod can be effectively improved, and the health of a smoker is facilitated. Therefore, the plasticizer can effectively reduce harmful ingredients in cigarette smoke, can also reduce the production cost of the filter rod, improves the curing efficiency, and has higher economic benefit.
In order to achieve the purpose, the invention is realized by the following technical scheme: on one hand, the invention provides a composite plasticizer which is prepared from the following raw materials in parts by weight: 16-90 parts of compound master batch, 13-40 parts of glycerol triacetate, 5-10 parts of phenol derivatives and 13-40 parts of auxiliary agents, wherein the compound master batch comprises at least two of polyol plasticizers, o-benzene plasticizers and citrate micromolecule plasticizers.
The current mechanism of plasticization of materials: by the blending method, the molecular chain segments of the plasticizer are inserted between the molecular chain segments of the polymer, the acting force between the macromolecular chain segments of the polymer is weakened, the mobility of the molecular chain segments of the polymer is increased, the obstacle of the movement of the molecular chain segments of the polymer is reduced, and the plasticity of the polymer is increased.
In a similar way, the plasticizer has the action principle that small molecular substances are added into the cellulose acetate fibers to reduce the Van der Waals force among or in the cellulose acetate molecules so as to improve the mobility of chain segments and molecular chains in the cellulose acetate, thereby reducing the production and processing temperature and improving the processing performance of the material. After the surface of the acetate fiber tows is dissolved and bonded by the plasticizer, the surface of the filter stick begins to be solidified, so that the hardness of the filter stick is obviously improved, and the filter stick with proper hardness is formed, so that the cigarette is not twisted or deformed in the processing and suction processes.
In order to reduce Van der Waals force among cellulose acetate molecules, the invention mixes the polyalcohol plasticizer, the phthalic plasticizer and the citrate micromolecule plasticizer to be used as a master batch, combines the triacetyl glycerine to be used as a composite plasticizer, and can effectively improve the physical properties of the cellulose acetate tows.
In the invention, the polyalcohol plasticizer is polyethylene glycol (PEG), and the polyethylene glycol (PEG) is an excellent chemical melting promoter. PEG is used as a plasticizer to be added into cellulose acetate, the molecular chain segment of PEG is long, the plasticizing effect of the cellulose acetate is mainly the solvation effect of PEG molecules and the dipole force effect of hydroxyl groups and other groups on the PEG, the PEG molecules can penetrate into the molecular chain segments of the cellulose acetate and form discrete connection points with the active center of the cellulose acetate molecules, but the quantity of the PEG penetrating into the molecular chain segments of the cellulose acetate can be gradually reduced along with the increase of the PEG dosage, one part of the molecular chain segment of the PEG penetrates into the molecular chains of the cellulose acetate, the other part of the molecular chain segment of the PEG is wound with the molecular chains of the cellulose acetate or the molecular chains of the PEG are wound together, so that the lubricating effect on the molecular chains of the cellulose acetate is weakened, and the bending performance of the cellulose acetate can be improved.
However, part of PEG is dissociated among the cellulose acetate molecules, and only the PEG is blended with the cellulose acetate, so that the plasticizing effect is poor and the performance is not stable enough. Therefore, the invention also adds the o-benzene plasticizer and the citrate micromolecule plasticizer to be compounded with PEG.
Preferably, the o-phthalic plasticizer includes at least one of dimethyl phthalate, diethyl phthalate, and dibutyl phthalate. The o-benzene plasticizer has good film forming property, adhesiveness and water resistance.
The invention adopts dimethyl phthalate to plasticize cellulose acetate, which is a plasticizer with strong dissolving power and can be compatible with various other plasticizers. Dimethyl phthalate is added into the plasticizer, so that the compatibility of PEG and citrate micromolecules can be improved, and the master batch is dispersed more uniformly. And the dimethyl phthalate can effectively improve the mechanical property of the cellulose acetate, increase the impact strength of the cellulose acetate, and also can ensure that the cellulose acetate has higher heat capacity, lower thermal expansion coefficient and thermal conductivity. Compared with the original cellulose, the cellulose acetate plasticized by dimethyl phthalate shows more uniform dispersity, higher Young modulus, higher thermal dimensional stability and lower thermal conductivity, and the subsequently prepared filter rod not only has excellent mechanical properties, but also has lower thermal conductivity, and can prevent the heat of cigarette combustion from being transferred to the mouth of a smoker.
Preferably, the citrate small molecule plasticizer comprises at least one of tri-n-butyl citrate, triethyl citrate and acetyl triethyl citrate.
The tri-n-butyl citrate has excellent compatibility with cellulose acetate, the curing rate of the plasticizer can be effectively improved by adding the tri-n-butyl citrate into the plasticizer, and the tri-n-butyl citrate is insoluble in water, nontoxic, odorless, low in volatility, heat-resistant, light-resistant and water-resistant, and has antibacterial property, nonirritant property, flame retardance and degradability.
Therefore, the compound master batch provided by the invention has good compatibility and high plasticizing efficiency; the plasticized acetate fiber filter rod has the advantages of good cold resistance, light resistance and water resistance, stable chemical performance, high environmental protection and long service life.
After the plasticizer is added, the surface of the acetate fiber tow is dissolved and bonded by the plasticizer, the surface of the filter stick begins to be solidified, so that the hardness of the filter stick is obviously improved, but the addition of the plasticizer possibly influences the whole adsorption capacity of the acetate fiber, and the invention also adds the phenol derivative capable of enhancing the harmful substance adsorption capacity.
Preferably, the phenolic derivative comprises at least one of clove oil, bay leaf oil and thyme oil.
Phenolic derivatives are phenolic containing compounds that have the potential for antioxidant activity due to their high reactivity for hydroxyl substitution and their ability to phagocytose free radicals. These compounds can be divided into two classes: flavonoids (extracts of pericarp, seed, stalk) and non-flavonoids (extracts of cellular vacuoles). The flavonoid compound constitutes a low molecular weight polyphenol group; they can be subdivided into flavones, flavonols and flavanones. Flavonoid compounds have a variety of biological effects, which due to their chelating properties, have anti-inflammatory, anti-allergic, antiviral and anti-cancer properties.
The addition of the phenol derivatives can obviously improve the adsorption and harm removal capacity of the plasticizer, and further improve the adsorption capacity of the filter rod. The effective component of the phenol derivative capable of reducing harmful substances in the smoke is an antioxidant. For example, the clove oil contains a large amount of eugenol, and eugenol molecules contain polyphenol hydroxyl groups, so that the eugenol has strong reducibility and has strong scavenging capacity on various oxygen free radicals, lipid free radicals and nitrogen free radicals. In addition, eugenol and other substances have synergistic antioxidation, and the synergistic effect is based on coupling oxidation of redox potential difference. On one hand, the coupling action reduces the potential difference between two substances in direct reaction, so that the reaction is easy to carry out; on the other hand, the oil-water distribution coefficients of the coupled antioxidants are complementary, and the functions of the antioxidants can be fully exerted.
But the compatibility of the phenol derivatives and the plasticizer is poor, the direct mutual dissolving effect is poor, and in order to achieve the using effect, a proper solvent is required to be added to dissolve the phenol derivatives, then the phenol derivatives are mixed with glycerol triacetate, and the mixture is added into a master batch to prepare the plasticizer with good dispersibility. The solvent chosen must meet the following three conditions: (1) the phenolic derivatives and the glycerol triacetate have better solubility; (2) the glycerol triacetate can be completely dissolved with glycerol triacetate and can be stably stored; (3) the solvent is safe, non-toxic and non-irritant, and can be safely applied to food, and the solvent must meet food sanitation regulations. Therefore, the invention adopts the glycol diacetate and the glycol as the solvent to dissolve the phenolic derivatives and mix with the glycerol triacetate according to the physical properties and chemical properties of the solvent.
Preferably, the auxiliary agent is a mixture of glycol diacetate and ethylene glycol.
Preferably, the mass ratio of the ethylene glycol diacetate to the ethylene glycol is 2: 3.
ethylene glycol is a good solvent and dissolves fibers and many other organic materials. The glycol has strong dissolving capacity, but is easy to metabolize and oxidize, so the invention uses the glycol and the glycol diacetate as the solvent. Glycol diacetate is an excellent, efficient, safe and nontoxic organic solvent, and particularly has extremely strong dissolving capacity for cellulose acetate.
Therefore, the addition of the plasticizer in the invention increases the water absorption rate of the cellulose acetate, increases the flexibility of the cellulose acetate, improves the elongation at break of the filter rod, reduces the glass transition temperature of the material by adding the plasticizer, widens the temperature range of the glass transition, can improve the mechanical property of the filter rod, and obviously improves the hardness of the filter rod, so that the filter rod with proper hardness is formed, the cigarette processing and suction processes are ensured not to be distorted and deformed, the connection characteristic of the filter rod and the cigarette can be improved, and the anti-heat collapse performance of the filter rod is improved.
On the other hand, the invention provides a preparation method of a composite plasticizer, which comprises the following specific steps: mixing 16-90 parts of compound master batch, 13-40 parts of glycerol triacetate, 5-10 parts of phenolic derivatives and 13-40 parts of auxiliary agent according to the weight ratio, and then placing the mixture in a high-speed mixer to stir for 2-3h to obtain the composite plasticizer.
Finally, the invention also provides application of the composite plasticizer, and the composite plasticizer is used for being added into the preparation process of the acetate fiber filter stick.
Preferably, the dosage of the composite plasticizer in the process of preparing the acetate fiber filter stick is 12-46%.
The invention has the following beneficial effects:
according to the composite plasticizer provided by the invention, the polyol plasticizer, the o-benzene plasticizer and the citrate micromolecule plasticizer are compounded to serve as the master batch, so that the curing time and the curing rate of the plasticizer can be greatly improved. And the phenol derivatives and the auxiliary agents are added into the master batch, so that the adsorbability of the filter rod can be effectively improved, and the health of a smoker is facilitated. Therefore, the plasticizer can reduce harmful ingredients in cigarette smoke, reduce the production cost of the filter rod, improve the curing efficiency and have higher economic benefit.
Drawings
FIG. 1 is a flow chart of a method for preparing a compounded plasticizer according to an embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention and the technical solutions in the prior art, the following will describe the specific embodiments of the present invention with reference to the accompanying drawings.
It is obvious that the drawings in the following description are only some examples of the invention, and it is obvious to a person skilled in the art that other drawings and other embodiments can be obtained from these drawings without inventive effort, and the invention is not limited to this example.
The specific embodiment of the invention is as follows:
example 1
The composite plasticizer is prepared from the following raw materials in parts by weight: 5 parts of dimethyl phthalate, 13 parts of polyethylene glycol, 13 parts of glycerol triacetate, 5 parts of clove oil, 5 parts of glycol diacetate and 8 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
5 parts of dimethyl phthalate, 13 parts of polyethylene glycol, 13 parts of glycerol triacetate, 5 parts of clove oil, 5 parts of glycol diacetate and 8 parts of ethylene glycol are mixed according to the weight ratio, and then the mixture is placed in a high-speed mixer to be stirred for 2 hours to obtain the composite plasticizer.
Example 2
The composite plasticizer is prepared from the following raw materials in parts by weight: 10 parts of diethyl phthalate, 30 parts of polyethylene glycol, 25 parts of glycerol triacetate, 8 parts of clove oil, 10 parts of glycol diacetate and 16 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
mixing 10 parts of dimethyl phthalate, 30 parts of polyethylene glycol, 25 parts of glycerol triacetate, 8 parts of clove oil, 10 parts of glycol diacetate and 16 parts of ethylene glycol according to the weight ratio, and then placing the mixture into a high-speed mixer to stir for 2.5 hours to obtain the composite plasticizer.
Example 3
The composite plasticizer is prepared from the following raw materials in parts by weight: 15 parts of dibutyl phthalate, 50 parts of polyethylene glycol, 40 parts of glycerol triacetate, 10 parts of clove oil, 16 parts of ethylene glycol diacetate and 24 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
mixing 15 parts of dimethyl phthalate, 50 parts of polyethylene glycol, 40 parts of glycerol triacetate, 10 parts of clove oil, 16 parts of glycol diacetate and 24 parts of ethylene glycol according to the weight ratio, and then placing the mixture into a high-speed mixer to stir for 3 hours to obtain the composite plasticizer.
Example 4
The composite plasticizer is prepared from the following raw materials in parts by weight: 8 parts of tri-n-butyl citrate, 8 parts of polyethylene glycol, 15 parts of glycerol triacetate, 5 parts of bay leaf oil, 5 parts of glycol diacetate and 8 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
mixing 8 parts of tri-n-butyl citrate, 8 parts of polyethylene glycol, 15 parts of glycerol triacetate, 5 parts of bay leaf oil, 5 parts of glycol diacetate and 8 parts of ethylene glycol according to the weight ratio, and then placing the mixture into a high-speed mixer to stir for 2 hours to obtain the composite plasticizer.
Example 5
The composite plasticizer is prepared from the following raw materials in parts by weight: 25 parts of triethyl citrate, 30 parts of polyethylene glycol, 25 parts of glycerol triacetate, 8 parts of bay leaf oil, 10 parts of glycol diacetate and 16 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
mixing 25 parts of tri-n-butyl citrate, 30 parts of polyethylene glycol, 25 parts of glycerol triacetate, 8 parts of bay leaf oil, 10 parts of glycol diacetate and 16 parts of ethylene glycol according to the weight ratio, and then placing the mixture into a high-speed mixer to stir for 2.5 hours to obtain the composite plasticizer.
Example 6
The composite plasticizer is prepared from the following raw materials in parts by weight: 40 parts of acetyl triethyl citrate, 50 parts of polyethylene glycol, 35 parts of glycerol triacetate, 10 parts of bay leaf oil, 16 parts of glycol diacetate and 24 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
mixing 40 parts of tri-n-butyl citrate, 50 parts of polyethylene glycol, 35 parts of glycerol triacetate, 10 parts of bay leaf oil, 16 parts of glycol diacetate and 24 parts of ethylene glycol according to the weight ratio, and then placing the mixture into a high-speed mixer to stir for 3 hours to obtain the composite plasticizer.
Example 7
The composite plasticizer is prepared from the following raw materials in parts by weight: 4 parts of dimethyl phthalate, 13 parts of tri-n-butyl citrate, 13 parts of glycerol triacetate, 5 parts of thyme oil, 5 parts of glycol diacetate and 8 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
4 parts of dimethyl phthalate, 13 parts of tri-n-butyl citrate, 13 parts of glycerol triacetate, 5 parts of thyme oil, 5 parts of glycol diacetate and 8 parts of glycol are mixed according to the weight ratio, and then the mixture is placed in a high-speed mixer to be stirred for 2 hours, thus obtaining the composite plasticizer.
Example 8
The composite plasticizer is prepared from the following raw materials in parts by weight: 13 parts of diethyl phthalate, 31 parts of triethyl citrate, 26 parts of glycerol triacetate, 8 parts of thyme oil, 10 parts of glycol diacetate and 16 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
13 parts of diethyl phthalate, 31 parts of triethyl citrate, 26 parts of glycerol triacetate, 8 parts of thyme oil, 10 parts of glycol diacetate and 16 parts of ethylene glycol are mixed according to the weight ratio, and then the mixture is placed in a high-speed mixer to be stirred for 2.5 hours to obtain the composite plasticizer.
Example 9
The composite plasticizer is prepared from the following raw materials in parts by weight: 21 parts of dibutyl phthalate, 50 parts of acetyl triethyl citrate, 40 parts of glycerol triacetate, 10 parts of thyme oil, 16 parts of glycol diacetate and 24 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
21 parts of dibutyl phthalate, 50 parts of acetyl triethyl citrate, 40 parts of glycerol triacetate, 10 parts of thyme oil, 16 parts of glycol diacetate and 24 parts of ethylene glycol are mixed according to the weight ratio, and then the mixture is placed in a high-speed mixer to be stirred for 3 hours to obtain the composite plasticizer.
Comparative example 1
On the basis of example 1, conventional glycerol triacetate is adopted to replace a compounded master batch as the condition of comparative example 1, and the plasticizer of comparative example 1 is prepared, which is as follows.
The composite plasticizer is prepared from the following raw materials in parts by weight: 31 parts of glycerol triacetate, 5 parts of clove oil, 5 parts of glycol diacetate and 8 parts of ethylene glycol.
In this example, the preparation process of the composite plasticizer is as follows:
31 parts of glycerol triacetate, 5 parts of clove oil, 5 parts of glycol diacetate and 8 parts of ethylene glycol are mixed according to the weight ratio, and then the mixture is placed in a high-speed mixer to be stirred for 2 hours to obtain the composite plasticizer.
Comparative example 2
On the basis of example 1, the phenolic derivative and the auxiliary were not added as the conditions of comparative example 2, and the plasticizer of comparative example 2 was prepared.
The composite plasticizer is prepared from the following raw materials in parts by weight: 5 parts of dimethyl phthalate, 13 parts of polyethylene glycol and 13 parts of glycerol triacetate.
In this example, the preparation process of the composite plasticizer is as follows:
5 parts of dimethyl phthalate, 13 parts of polyethylene glycol and 13 parts of glycerol triacetate are mixed according to the weight ratio, and then the mixture is placed in a high-speed mixer to be stirred for 2 hours, so that the composite plasticizer is obtained.
Test example 1
The composite plasticizers prepared in examples 1-9 and comparative examples 1-2 are named by numbers, and then the plasticizers are respectively used in the preparation process of the corresponding acetate fiber filter rods, and the dosage of the composite plasticizer is 20% of the acetate fibers.
The specific processing steps of the acetate fiber filter rod are as follows:
the first step is as follows: melting acetate fibers, adding a composite plasticizer, uniformly stirring, placing the molten material in a microwave environment, performing microwave radiation treatment, extruding through a spinneret plate, cooling, winding, drafting, curling and drying to obtain tows;
the second step is that: and (3) placing the tows prepared in the first step into a filter stick forming machine for forming, loosening the tows, spraying an adhesive on the loosened tows, rolling and forming by adopting forming paper, cutting into cigarette filter tips with a specified length, and drying to obtain the cigarette filter tips.
Note: in the above process of preparing a cigarette filter:
the microwave radiation treatment conditions adopted are as follows: the frequency of the microwave is about 2.5GHz, the power is about 220W, and the processing time is about 20 min; in the extrusion process of the spinneret plate, the number of the adopted spinneret plate holes is about 25000, the spinneret holes are hollow spinneret holes, the titer of each monofilament can be set to be 3D, and the area ratio of the monofilament body to the hollow area on the section of each monofilament is about 2: 1; wherein, the cooling is to cool the newly spun tows by adopting an air cooling method, and the cooling air temperature is normal temperature; the winding rate can be set to about 280 m/min; the drawing is to draw the tow in a water bath environment, wherein the drawing strength can be set to 1.2CN/dtex, the drawing degree is about 25%, and the water bath temperature is about 70 ℃.
Wherein, when opening the tows, the pressure of the opening roller can be set to about 0.2MPa, and the roller speed ratio (opening ratio) of the two opening rollers can be set to about 1: 1.5.
according to GB/T22838-2009 test standards, the filter rods corresponding to the composite plasticizers prepared in examples 1-9 and comparative examples 1-2 are subjected to corresponding performance tests, and the test results are shown in the following table 1.
TABLE 1 results of performance test of filter rods corresponding to the compounded plasticizers obtained in examples 1 to 9 and comparative examples 1 to 2
The test results in table 1 show that the filter stick plasticized by the composite plasticizer prepared in example 1 has better suction resistance, hardness, roundness and thermal shrinkage than those of the filter stick prepared in comparative example 1, and the addition of the composite master batch prepared by the invention into acetate fibers as the plasticizer can not only improve the mechanical properties of the filter stick and obviously improve the hardness of the filter stick, thereby forming the filter stick with proper hardness, ensuring that no distortion and deformation are generated in the cigarette processing and suction processes, but also improving the tipping characteristics of the filter stick and the cigarette and improving the anti-thermal collapse performance of the filter stick.
Compared with the comparative example 2 and the example 1, the filter stick prepared by the composite plasticizer without the phenolic derivative and the auxiliary agent has obviously weaker adsorption capacity on harmful substances, and the addition of the phenolic derivative can improve the adsorption and harm removal capacity of the plasticizer and further improve the adsorption capacity of the filter stick.
Therefore, the composite plasticizer provided by the invention can better solve the problems of the conventional plasticizer glyceryl triacetate, effectively reduce harmful ingredients in cigarette smoke, reduce the production cost of a filter rod, improve the curing efficiency and have higher economic benefit.
The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present invention.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the specific embodiments of the invention be limited to these descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. The composite plasticizer is characterized by being prepared from the following raw materials in parts by weight: 16-90 parts of compound master batch, 13-40 parts of glycerol triacetate, 5-10 parts of phenol derivatives and 13-40 parts of auxiliary agents, wherein the compound master batch comprises at least two of polyol plasticizers, o-benzene plasticizers and citrate micromolecule plasticizers.
2. The composite plasticizer according to claim 1, wherein said polyol plasticizer is polyethylene glycol.
3. The composite plasticizer according to claim 1, wherein the ortho-benzene plasticizer comprises at least one of dimethyl phthalate, diethyl phthalate, and dibutyl phthalate.
4. The composite plasticizer according to claim 1, wherein the citrate-based small molecule plasticizer comprises at least one of tri-n-butyl citrate, triethyl citrate, and acetyl triethyl citrate.
5. The composite plasticizer according to claim 1, wherein the phenolic derivative comprises at least one of clove oil, bay leaf oil, thyme oil.
6. The composite plasticizer according to claim 1, wherein the auxiliary agent is a mixture of ethylene glycol diacetate and ethylene glycol.
7. The composite plasticizer according to claim 6, wherein the mass ratio of the ethylene glycol diacetate to the ethylene glycol is 2: 3.
8. the preparation method of the composite plasticizer according to any one of claims 1 to 7, which is characterized by comprising the following specific steps: mixing 16-90 parts of compound master batch, 13-40 parts of glycerol triacetate, 5-10 parts of phenolic derivatives and 13-40 parts of auxiliary agent according to the weight ratio, and then placing the mixture in a high-speed mixer to stir for 2-3h to obtain the composite plasticizer.
9. The use of a compounded plasticizer according to claim 1 for addition to the manufacture of filter rods of cellulose acetate.
10. The use of the composite plasticizer according to claim 9, wherein the amount of the composite plasticizer used in the process of preparing the acetate fiber filter stick is 12-46%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115058122A (en) * | 2022-07-20 | 2022-09-16 | 湖北中烟工业有限责任公司 | Plasticizer of acetate fiber tow for cigarette and acetate fiber filter rod for cigarette |
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Application publication date: 20220524 |