CN103788387A - Preparation method of low-VOC polypropylene resin - Google Patents
Preparation method of low-VOC polypropylene resin Download PDFInfo
- Publication number
- CN103788387A CN103788387A CN201210421186.9A CN201210421186A CN103788387A CN 103788387 A CN103788387 A CN 103788387A CN 201210421186 A CN201210421186 A CN 201210421186A CN 103788387 A CN103788387 A CN 103788387A
- Authority
- CN
- China
- Prior art keywords
- acrylic resin
- preparation
- low voc
- ultrasonic extraction
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a preparation method of a low-VOC polypropylene resin. The preparation method comprises a step that ultrasonic extraction pretreatment of a raw material polypropylene resin is carried out in a water bath at 40-120DEG C, wherein the sound frequency is 20-160KHz, and the sound power density is 0.35-5W/cm<2>. The ultrasonic pretreatment of the polypropylene resin substantially reduces the content of total volatile organic compounds (TVOCs) in a polypropylene material, and makes the TVOCs of the polypropylene resin to be lower than 50mug.C/g, so the residual problem of the VOCs in the polypropylene resin is solved.
Description
Technical field
The preparation method who the present invention relates to a kind of acrylic resin, says further, relates to a kind of preparation method of low VOC acrylic resin.
Background technology
Polypropylene (PP) is because of the feature of its high comprehensive performance, wide material sources, super quality and competitive price, widespread use every field.But polypropylene is affected by the factors such as the residual and short chain oligomer of catalyzer and polymerization technique and oxide compound, and the effect of the various additives that add in follow-up modifying process, existing polypropylene material and goods all exist and discharge to some extent volatile organic matter (VOC) contaminate environment and the healthy problem of harm people.This has limited the application of polypropylene material in fields such as environmental requirement higher high-grade automotive upholstery, medical and packaging materials for food to a great extent.Therefore, research and develop the requirement that the low VOC acrylic resin of environment-friendly type and material could be expanded polyacrylic Application Areas and meet green material.
At present, in abroad for reducing polypropylene material, the method for VOC mainly contains following three kinds:
1, add sorbent material.The method is mainly added the physical absorbents such as gac, porous silica, activated alumina, clay, wilkinite, many csa molecules sieve in polypropylene, and by screw extrusion press extruding pelletization under certain processing condition.As Chinese patent CN 1727389A, CN 1727390A, CN101817953A, CN101928429A, CN102020809A etc.But the product that this method makes exists the problem of adsorption equilibrium, at higher temperature, balance moves to the direction of desorption, causes volatilizable organic volatilization problem, still has the hidden danger that in polypropylene material, the VOC later stage discharges again.
2, add photocatalyst.As Chinese patent CN 101570612A decomposes organic molecule and falls low VOC content by adding a kind of inorganic photocatalyst, but have the problem of photocatalysis efficiency, and its effect is limited.
3, devolatilization.Mainly utilize professional devolatilization equipment and process in polymerization process and the course of processing, to carry out devolatilization.Wherein devolatilization in polymerization process, efficiency is higher, but due to the limitation of its production technology and equipments, cost is higher, is difficult for widespread use; In the course of processing, devolatilization mainly utilizes degassing extruder to carry out melt devolatilization.If Chinese patent (CN101255252B) is by adding expellent as sodium bicarbonate, Magnesium hydrogen carbonate, Calcium hydrogen carbonate, water, lower boiling fatty alcohol etc., reduce the VOC of material.But the more difficult stable dispersion of expellent that the method is added is in PP melt; And three grades vacuumize minimizing working lipe that makes expellent have system, and devolatilization efficiency is not high; In addition, by after being mixed together with unclassified stores from the same charging opening blanking of forcing machine, can cause expellent to heat in advance volatilization at feeding section or solid conveying section, drive away effect thereby further subdue its VOC.
Summary of the invention
For problems of the prior art, the invention provides a kind of preparation method of acrylic resin of low volatilizable organic content.Can reduce quickly and effectively polyacrylic VOC total amount, solve well the problem of prior art.
The object of this invention is to provide a kind of preparation method of low VOC acrylic resin.
Preparation method of the present invention, comprises that by raw material acrylic resin, through ultrasonic extraction pre-treatment, wherein ultrasonic extraction carries out in water-bath.The frequency of sound wave of the ultrasonic extraction adopting is chosen as 20KHz ~ 160KHz, preferably 25KHz ~ 100KHz; Acoustic power density is 0.35W/cm
2~ 5W/cm
2, preferably 0.5 ~ 3W/cm
2; Extraction temperature is 40 ~ 120 ℃, preferably 60 ~ 90 ℃.
In addition, the extraction treatment time does not need to be particularly limited, but generally can be 10min ~ 300min, and preferably extraction time is 30min ~ 240min.
Described ultrasonic extraction adopts existing various ultrasonic cleaning apparatus in prior art, preferred industrial ultrasonic cleaner.
Specifically, the preparation method of low VOC acrylic resin provided by the invention, be achieved through the following technical solutions: first by the ultrasonic extraction pre-treatment under above-mentioned condition in water-bath of raw material acrylic resin, then by the polypropylene of processing in vacuum-drying.Now gained polypropylene has been low VOC acrylic resin.A more progressive ground, according to actual needs, finally carries out above-mentioned dried acrylic resin and processing aid melt blending extruding pelletization and makes low VOC acrylic resin.
Above-described processing aid, according to the needs of the concrete processing of acrylic resin, in blend material, add conventional processing aid in acrylic resin modification prior art, for example: oxidation inhibitor, lubricant, static inhibitor, dispersion agent, pigment etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
The preparation method of low VOC acrylic resin of the present invention, preferably can comprise the following steps:
The 1st step: raw material polypropylene is placed on to the polypropylene that obtains low VOC in water-bath through ultrasonic extraction; The frequency of sound wave of ultrasonic extraction is chosen as 20KHz ~ 160KHz, preferably 25KHz ~ 100KHz; Acoustic power density is 0.35W/cm
2~ 5W/cm
2, preferably 0.5 ~ 3W/cm
2; Extraction temperature is 40 ~ 120 ℃, preferably 60 ~ 90 ℃.The extraction treatment time is 10min ~ 300min, and preferably extraction time is 30min ~ 240min.
The 2nd step: pretreated ultrasonic extraction acrylic resin, processing aid etc. are fully mixed by required component proportion in interior each component in mixing equipment, obtain pre-composition.
The 3rd step: the pre-composition of step 2 be can be made into low VOC acrylic resin of the present invention from the charging opening blanking of melt blending equipment after melt blending.In order better to remove VOC, the vacuum tightness that this step preferably keeps melt blending device vacuum system-more than 0.05MPa, more preferably-more than 0.08MPa.
The mixing equipment of material various mixing equipments used in can adopting prior art in the preparation method of the invention described above, as stirrer, kneading machine etc.The melt blending equipment using in aforesaid method of the present invention is the general blending equipment in rubber and plastic processing industry, can be screw extrusion press, the mixing unit of BUSS etc.
In the preparation of low VOC acrylic resin of the present invention, material melt blending temperature is blending temperature used in common polypropylene processing, should in the scope of its decomposition, select not only guaranteeing the complete melting of matrix resin but also can not make, be generally 190 ℃ ~ 230 ℃, preferred processing temperature is 200 ~ 230 ℃; If employing screw extrusion press, its screw speed is generally 300 ~ 450rpm.
Compared with prior art, the present invention has following beneficial effect:
In the preparation method of low VOC acrylic resin of the present invention, in order better to remove the VOC in polypropylene, by raw material polypropylene through ultrasonic extraction processing, utilize hyperacoustic " cavitation " effect, remove a large amount of VOC residual in acrylic resin, remove the content of VOC in acrylic resin from source.
The total volatile organism (TVOC) of acrylic resin of the present invention can significantly reduce, more preferably, TVOC can be lower than 50 μ gC/g, the deficiencies in the prior art are solved well, operating procedure is simple and reliable, input cost is lower, is applicable to the fields such as the higher high-grade automotive upholstery of environmental requirement, medical and packaging material for food.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.Following examples are only for further illustrating of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field makes the present invention according to following content and adjustment still belong to protection scope of the present invention.
Embodiment 1 ~ 12
By raw material polypropylene: polypropylene powder (092B, pilot scale base, Beijing Chemical Research Institute produce) in water-bath through industrial ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.) ultrasonic extraction, then polypropylene powder is placed on to vacuum-drying in vacuum drying oven and obtains dry polypropylene powder; Afterwards the polypropylene powder of processing and processing aid (oxidation inhibitor B225, BASF Aktiengesellschaft) etc. are put into homogenizer, under the rotating speed of 300 revs/min, stir 3 minutes, each component is fully mixed; Subsequently said mixture material is added from opening for feed, through the mixing unit of BUSS (MKD-30, BUSS company of Switzerland) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains low VOC acrylic resin.Its concrete formula and processing parameter are in table 1, and wherein each component concentration is all in parts by weight.
The pellet of extruding is dried to 2h in 80 ℃ of constant temperature ovens, and the test of TVOC is according to the standard VDA277 test of German automobiles industrial combination meeting.Specific performance the results are shown in Table 1.
Comparative example 1
Pre-treatment by polypropylene powder (with embodiment 1) without ultrasonic extraction, direct and described processing aid (with embodiment 1) is put into homogenizer together, stirs 3 minutes under the rotating speed of 300 revs/min, and each component is fully mixed.Subsequently by said mixture material through the mixing unit of BUSS (with embodiment 1) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains acrylic resin.Specifically formula, processing parameter and results of property are in table 1 for it, and wherein each component concentration is all in parts by weight.
Comparative example 2
Polypropylene powder (with embodiment 1) is soaked to 120min in 70 ℃ of water-baths, and directly taking-up is placed on vacuum-drying in baking oven and obtains dry acrylic resin afterwards; Afterwards the polypropylene powder of so processing and processing aid (with embodiment 1) etc. are put into homogenizer, under the rotating speed of 300 revs/min, stir 3 minutes, each component is fully mixed.Subsequently by said mixture material through the mixing unit of BUSS (with embodiment 1) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains acrylic resin.Specifically formula, processing parameter and results of property are in table 1 for it, and wherein each component concentration is all in parts by weight.
Comparative example 3 ~ 8
By step the same manner as in Example 1 polypropylene powder (with embodiment 1), through ultrasonic extraction pre-treatment, the part processing parameter of just processing is different from scope of the presently claimed invention; This polypropylene powder and described processing aid (with embodiment 1) etc. are put into homogenizer, under the rotating speed of 300 revs/min, stir 3 minutes, each component is fully mixed.Subsequently by said mixture material through the mixing unit of BUSS (with embodiment 1) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains acrylic resin.It is specifically filled a prescription, processing parameter is in table 1, and wherein each component concentration is all in parts by weight.
The pellet of extruding is dried to 2h in 80 ℃ of constant temperature ovens, and the test of TVOC is according to the standard VDA277 test of German automobiles industrial combination meeting.Specific performance the results are shown in Table 1.
Embodiment 13 ~ 24
By raw material polypropylene: acrylic resin (K9026, Sinopec Yanshan Mountain branch office) in water-bath through industrial ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.) ultrasonic extraction, then polypropylene is placed on to vacuum-drying in baking oven and obtains dry acrylic resin; Afterwards the acrylic resin of processing and processing aid (with the oxidation inhibitor B225 of embodiment 1) etc. are put into homogenizer, under the rotating speed of 300 revs/min, stir 3 minutes, each component is fully mixed; Subsequently said mixture material is added from major ingredient mouth, through the mixing unit of BUSS (MKD-30, BUSS company of Switzerland) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains low VOC acrylic resin.Its concrete formula and processing parameter are in table 2, and wherein each component concentration is all in parts by weight.
The pellet of extruding is dried to 2h in 80 ℃ of constant temperature ovens, and the test of TVOC is according to the standard VDA277 test of German automobiles industrial combination meeting.Specific performance the results are shown in Table 2.
Comparative example 9
Pre-treatment by acrylic resin (with embodiment 13) without ultrasonic extraction, direct and described processing aid (with embodiment 13) is put into homogenizer together, stirs 3 minutes under the rotating speed of 300 revs/min, and each component is fully mixed.Subsequently by said mixture material through the mixing unit of BUSS (with embodiment 13) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains acrylic resin.Specifically formula, processing parameter and results of property are in table 2 for it, and wherein each component concentration is all in parts by weight.
Comparative example 10
Acrylic resin (with embodiment 13) is soaked to 120min in 60 ℃ of water-baths, and directly taking-up is placed on vacuum-drying in baking oven and obtains dry acrylic resin afterwards; Afterwards the acrylic resin of so processing and processing aid (with embodiment 13) etc. are put into homogenizer, under the rotating speed of 300 revs/min, stir 3 minutes, each component is fully mixed.Subsequently by said mixture material through the mixing unit of BUSS (with embodiment 13) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains acrylic resin.Specifically formula, processing parameter and results of property are in table 2 for it, and wherein each component concentration is all in parts by weight.
Comparative example 11 ~ 16
By polypropylene powder (with embodiment 1) with the step embodiment 13 through ultrasonic extraction pre-treatment, the part processing parameter of just processing is different from scope of the presently claimed invention; This acrylic resin and described processing aid (with embodiment 13) etc. are put into homogenizer, under the rotating speed of 300 revs/min, stir 3 minutes, each component is fully mixed.Subsequently by said mixture material through the mixing unit of BUSS (with embodiment 13) within the scope of 190 ℃ ~ 220 ℃, melt blending extruding pelletization under the condition that keeps vacuum tightness-0.08MPa, obtains acrylic resin.It is specifically filled a prescription, processing parameter is in table 2, and wherein each component concentration is all in parts by weight.
The pellet of extruding is dried to 2h in 80 ℃ of constant temperature ovens, and the test of TVOC is according to the standard VDA277 test of German automobiles industrial combination meeting.Specific performance the results are shown in Table 2.
Table 1
Table 2
As can be seen from the above table, polypropylene is adopted to the pretreated method of ultrasonic extraction of the present invention, can significantly reduce the content of VOC in acrylic resin, make the total volatile organism (TVOC) of acrylic resin lower than 50 μ gC/g.
Claims (9)
1. a preparation method for low VOC acrylic resin, comprises that by raw material acrylic resin, through ultrasonic extraction pre-treatment, wherein ultrasonic extraction carries out in water-bath; Frequency of sound wave is chosen as 20KHz ~ 160KHz; Acoustic power density is 0.35W/cm
2~ 5W/cm
2; Extraction temperature is 40 ~ 120 ℃.
2. the preparation method of low VOC acrylic resin according to claim 1, is characterized in that:
The frequency of sound wave of described ultrasonic extraction is chosen as 25KHz ~ 100KHz.
3. the preparation method of low VOC acrylic resin according to claim 1, is characterized in that:
The acoustic power density of described ultrasonic extraction is 0.5 ~ 3W/cm
2.
4. the preparation method of low VOC acrylic resin according to claim 1, is characterized in that:
The temperature of described ultrasonic extraction is 60 ~ 90 ℃.
5. the preparation method of low VOC acrylic resin according to claim 1, is characterized in that:
The extraction treatment time of described ultrasonic extraction is 10min ~ 300min.
6. the preparation method of low VOC acrylic resin according to claim 5, is characterized in that:
The extraction treatment time of described ultrasonic extraction is 30min ~ 240min.
7. according to the preparation method of low VOC acrylic resin described in claim 1 ~ 6, it is characterized in that:
Raw material polypropylene is placed on to the ultrasonic extraction under described condition in water-bath, afterwards that the polypropylene vacuum of treated mistake is dry.
8. the preparation method of low VOC acrylic resin according to claim 7, is characterized in that:
Make described low VOC acrylic resin through vacuum drying acrylic resin, processing aid in interior component melts blend by comprising described ultrasonic extraction after pretreated.
9. the preparation method of low VOC acrylic resin according to claim 8, is characterized in that:
In described melt blending process, keep the vacuum system vacuum tightness of melt blending equipment be-more than 0.05MPa, to be preferably-more than 0.08MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210421186.9A CN103788387B (en) | 2012-10-29 | 2012-10-29 | A kind of preparation method of low VOC acrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210421186.9A CN103788387B (en) | 2012-10-29 | 2012-10-29 | A kind of preparation method of low VOC acrylic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103788387A true CN103788387A (en) | 2014-05-14 |
| CN103788387B CN103788387B (en) | 2016-02-24 |
Family
ID=50664470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210421186.9A Active CN103788387B (en) | 2012-10-29 | 2012-10-29 | A kind of preparation method of low VOC acrylic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103788387B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652532A (en) * | 2016-07-25 | 2018-02-02 | 中国石油化工股份有限公司 | A kind of low VOC preparation method of acrylic resin and its acrylic resin of preparation |
| CN109822856A (en) * | 2019-03-22 | 2019-05-31 | 神华(北京)新材料科技有限公司 | A kind of extruder and method preparing low smell polyolefine material |
| CN112693020A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Polypropylene resin with low VOC content and preparation method thereof |
| CN114456411A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Polypropylene resin with low VOC content and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412123A (en) * | 2002-12-09 | 2003-04-23 | 南京大学环境学院 | Method for blowing and removing volatile pollutant in waste water by using ultrasonic wave |
-
2012
- 2012-10-29 CN CN201210421186.9A patent/CN103788387B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412123A (en) * | 2002-12-09 | 2003-04-23 | 南京大学环境学院 | Method for blowing and removing volatile pollutant in waste water by using ultrasonic wave |
Non-Patent Citations (1)
| Title |
|---|
| 周茹英: ""超声波强化聚乙烯脱挥研究"", 《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》, 15 September 2004 (2004-09-15) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652532A (en) * | 2016-07-25 | 2018-02-02 | 中国石油化工股份有限公司 | A kind of low VOC preparation method of acrylic resin and its acrylic resin of preparation |
| CN109822856A (en) * | 2019-03-22 | 2019-05-31 | 神华(北京)新材料科技有限公司 | A kind of extruder and method preparing low smell polyolefine material |
| CN112693020A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Polypropylene resin with low VOC content and preparation method thereof |
| CN114456411A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Polypropylene resin with low VOC content and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103788387B (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788387B (en) | A kind of preparation method of low VOC acrylic resin | |
| US20120004331A1 (en) | Automatic rubber powder plasticizing process and apparatus thereof | |
| CN104785101B (en) | Purification system for removing VOCs from air | |
| CN106432614B (en) | A method of promoting polyolefin graft reaction | |
| CN103539896A (en) | Novel high-grafting-ratio low-gel polyethylene compatilizer and preparation method thereof | |
| CN105664881A (en) | Compound adsorbent for water treatment | |
| CN106496610B (en) | A kind of tenacity increased nylon and nylon toughener and preparation method | |
| CN103709557A (en) | Recycling method of waste diatomite filter cakes in plasticizer factory | |
| CN104801283B (en) | A kind of preparation method for the compound adsorbent of VOCs in purify air | |
| CN100366675C (en) | Method for preparing defoaming, dehumidifying and drying mother stock for ABS(acrylonitrile- butadiene-styrene copolymer) plastic processing | |
| CN102000541B (en) | Spongy bentonite-based composite adsorbing material and preparation method thereof | |
| CN106566070A (en) | Modified polypropylene material and preparation method thereof | |
| CN105731562A (en) | Sewage treatment agent for printing and dyeing industry and preparation method of sewage treatment agent | |
| CN102532793B (en) | Plastic grain-removal brightener and preparation method thereof | |
| CN103709496A (en) | Low-VOC polypropylene composition and preparation method thereof | |
| CN104229769B (en) | A kind of preparation method of porous carbon materials | |
| EA201170990A1 (en) | COMPOSITES CONTAINING POLYMER AND SELECTED LAYERED COMPOUND, AND METHODS FOR THEIR PREPARATION AND APPLICATION | |
| CN104788617A (en) | Method for reducing color number of cyclopentadiene petroleum resin | |
| CN112693020A (en) | Polypropylene resin with low VOC content and preparation method thereof | |
| CN103304893A (en) | Low VOC (Volatile Organic Compound) polypropylene composition and preparation method thereof | |
| CN107815123A (en) | Organic reinforced type silicon rubber foam material and preparation method thereof | |
| CN104744004A (en) | Preparation method of aerating concrete building block | |
| CN103304892A (en) | VOC (Volatile Organic Compounds)-inhibited master batch for polypropylene, and preparation method and applications thereof | |
| CN102219212B (en) | Manufacture method for molded part of foamed active electrical carbon material | |
| CN105540583A (en) | Preparation method of activated carbon ceramic composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |