WO2014098360A1 - Method for preparing vinyl chloride-based resin by using suspension polymerization - Google Patents
Method for preparing vinyl chloride-based resin by using suspension polymerization Download PDFInfo
- Publication number
- WO2014098360A1 WO2014098360A1 PCT/KR2013/009113 KR2013009113W WO2014098360A1 WO 2014098360 A1 WO2014098360 A1 WO 2014098360A1 KR 2013009113 W KR2013009113 W KR 2013009113W WO 2014098360 A1 WO2014098360 A1 WO 2014098360A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl chloride
- temperature
- polymerization
- reaction
- resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
Definitions
- the present invention relates to a method for producing a vinyl chloride-based resin, and more particularly, by gradually increasing the polymerization temperature by a predetermined temperature per minute at the time of the pressure drop in the second half of the reaction during the production of the vinyl chloride-based resin to prevent pressure drop and foam generation. It relates to a method for producing a vinyl chloride-based resin to improve the quality of the projections and to improve the quality by solving the thermal stability of the residual initiator.
- Vinyl chloride-based resins are inexpensive and have excellent processability, chemical resistance, durability, insulation properties, and are widely used as hard and soft materials such as pipes, wallpaper, window frames, wire coatings, wrap films, and sheets.
- vinyl chloride-based resins are widely used, customer's eye level on molding processing has been increased, and improvement of molding processability is continuously required.
- the processability of the vinyl chloride-based resin is affected by the internal porosity, particle diameter, particle distribution, and morphology of the particles and is intended to increase the meltability of the resin.
- One of the quality criteria for evaluating the melting characteristics of these resins is called protrusions or fish-eyes, which can confirm the difference in the degree of melting and the quality of the final product.
- the difference in the meltability of the particles is suspected as a cause of the deterioration of the protrusion quality, and the production of such unmelted particles may be associated with the foam generated during the reaction.
- foam is generated by crossing the high usage and pressure drop of the reflux condenser at the end of the reaction, and the dry foam containing the particles floats to the top of the reactor and to the reflux condenser.
- the particles floated by the foam remain inside the reactor and the reflux condenser, and are subjected to repolymerization as they are included in the next reaction to generate large, low internal porosity particles.
- the production of particles of low meltability deteriorates the projection quality.
- a method for inhibiting foam generation during a reaction may be used alone or by using an antifoaming agent with other additives.
- Methods have been used to suppress the occurrence of foam by mixing.
- antifoaming agent alone.
- In order to add antifoaming agents and additives during the reaction there are economic problems such as investment in equipment and the price of the amount of antifoaming agent and additives added. There is a problem of deterioration.
- An object of the present invention is to solve the problems of the prior art, the present invention is to increase the polymerization temperature by a predetermined temperature per minute from the reference temperature at the time when the pressure drop occurs at the end of the reaction to prevent the pressure drop and foam generation repolymerization And scale generation.
- the present invention induces decomposition of the initiator by the elevated temperature to lower the content of the initiator remaining after the end of the reaction to produce a vinyl chloride-based resin with less projections and excellent thermal stability, so the problem of scale generation of the existing method
- An object of the present invention is to provide a method for producing a resin without quality problems due to protrusions and thermal stability.
- the present invention is a method for producing a vinyl chloride resin by suspension polymerization, the polymerization temperature of the vinyl chloride resin, characterized in that to increase the temperature from the time point at which the pressure is reduced at the end of the reaction It provides a manufacturing method.
- the present invention after the start of the suspension polymerization reaction from the time when the reaction pressure is lowered more than 0.01 kgf / cm 2 to less than 0.5 kgf / cm 2 , at a temperature rising rate of more than 0.008 °C / min to less than 0.8 °C / min, more than 10 minutes It provides a method for producing a vinyl chloride-based resin, characterized in that to increase the temperature for less than 90 minutes.
- the decreasing reaction pressure is characterized in that more than 0.01 kgf / cm 2 to less than 0.2 kgf / cm 2 as an example.
- the temperature increase rate is, for example, characterized in that more than 0.008 °C / min less than 0.65 °C / min.
- the temperature increase rate is characterized by adjusting the temperature control system as an example.
- the reaction temperature of the polymerization is characterized in that within 30 to 80 °C range, for example.
- the temperature increase time is, for example, characterized in that 30 to 60 minutes.
- the present invention provides a vinyl chloride-based resin prepared by the method for producing a vinyl chloride-based resin.
- the vinyl chloride-based resin for example, is characterized in that the residual initiator concentration is less than 0.002 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.
- the present invention provides a vinyl chloride-based resin composition
- a vinyl chloride-based resin composition comprising the vinyl chloride-based resin, inorganic filler and stabilizer.
- the inorganic filler is characterized in that the carbon black as an example.
- the vinyl chloride-based resin composition is characterized in that the number of fish-eyes (thickness 0.3 mm, area 400 cm 2 ) is less than 10.
- the present invention is a vinyl chloride system, characterized in that the temperature rises for 20 to 60 minutes at a temperature increase rate of 0.01 to 0.5 °C / min from the time when the reaction pressure is lowered from 0.05 to 0.1 kgf / cm 2 after starting the suspension polymerization reaction It provides a method for producing a resin.
- the method of the present invention in the step of preparing the vinyl chloride-based resin by suspension polymerization, it is possible to control the temperature increase rate for each polymerization temperature and to prevent the pressure drop at the end of the reaction, thereby increasing the reflux condenser. It has the advantage of suppressing the foam generation appearing while overlapping the heat removal point. In addition, it is possible to solve the problem of protrusion quality and thermal stability due to the conventional scale problem and repolymerization problem.
- the present invention in order to solve the disadvantages of the prior art, by raising the temperature gradually at the time of the end of the pressure drop occurs to prevent the pressure drop, the possibility of foam that can occur at the time of the intersection of the high amount of reflux condenser and the pressure drop It provides a method for producing a resin that is removed, and induces decomposition of the initiator remaining at the end of the reaction to improve the quality after the reaction.
- foam does not occur after the reaction to prevent the inflow of particles that can be repolymerized in the next reaction, and the residual initiator is not left so that the thermal stability is simultaneously improved, thereby improving quality.
- the present invention in the method for producing a vinyl chloride-based resin by suspension polymerization while adding different polymerization temperatures and different polymerization initiators according to the degree of polymerization, in order to minimize the generation of foam generated during the reaction and to minimize the content of the residual initiator It provides a method of producing a vinyl chloride-based resin, characterized in that the polymerization temperature is raised by a predetermined temperature per minute to prevent the pressure drop appearing at the end of the reaction to control the generation of foam.
- the amount of defrosting by the reflux condenser is increased at the end of the reaction of the prior art and the polymerization conversion rate is increased, and a dry foam containing particles is generated at the end of the pressure drop at the end of the reaction. It is a technical feature to provide a new method for producing a vinyl chloride-based resin that can overcome the problems of quality improvement by solving the problem that repolymerization occurs, and solve the high level of residual initiator.
- the meltability of the final resin obtained can be improved.
- it can raise a temperature below 0.01 degreeC-0.65 degreeC or 0.02 degreeC-0.65 degreeC, More preferably, 0.05 degreeC-0.6 degreeC.
- the time for raising the temperature at the time of pressure decrease caused the reaction end is described in the time shown is about 0.01kgf / cm 2 to less than 0.5kgf / cm 2 the pressure drop.
- the temperature is increased at a pressure drop time of 0.05 to less than 0.2 kgf / cm 2 . If the temperature is raised before the pressure drop in the above range, a pressure change may occur to the elevated temperature, resulting in unstable quality problems, and if the temperature is increased after the pressure drop exceeds the above range, the heat removal amount and the pressure drop of the reflux condenser are Since foam containing particles is generated, this causes protrusions and internal scales of the reactor, which adversely affects it.
- the polymerization temperature is generally determined by the degree of polymerization of the resin, and the temperature generally applied is 55 to 60 ° C. for the number average degree of polymerization of 1000 products, 61 to 65 ° C. for the number average degree of polymerization of 800 products and 700 number average degree of polymerization of the products. In the case of it is determined in the range of 66 to 70 °C.
- the polymerization temperature in this invention satisfy
- the degree of polymerization refers to the number of repeated units, ie units or monomers, constituting the polymer, and the number average degree of polymerization is used in the present invention.
- reaction pressure also varies depending on the polymerization temperature, the degree to which the pressure falls is also different. Accordingly, it is possible to control the temperature increase rate according to the difference in the pressure decreases at the end of the reaction according to the polymerization temperature, so that the reaction stability does not have a burden on the reaction stability.
- the pressure drop occurs to increase the temperature at the existing polymerization temperature for 30 minutes to 60 minutes, preferably 30 minutes to 50 minutes, even more preferably 30 minutes to 40 minutes after the pressure drop occurs.
- Suitable initiators in the above polymerizations are as follows.
- the amount of the polymerization initiator to be injected into the reactor is characterized in that the same amount as the polymerization initiator used in the conventional polymerization, it is characterized in that 0.02 to 0.3 parts by weight, or 0.03 to 0.2 parts by weight based on 100 parts by weight of the vinyl chloride monomer As another example, use of 0.04 to 0.15 parts by weight is appropriate.
- the present invention provides a vinyl chloride-based resin, characterized in that it is prepared by the method for producing a vinyl chloride-based resin as described above.
- the vinyl chloride-based resin has a residual initiator concentration of less than 0.002 parts by weight, or 0.0005 to 0.0015 parts by weight, more preferably 0.0006 to 0.001 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.
- the vinyl chloride-based resin of the present invention is a copolymer of a vinyl chloride monomer composed mainly of a vinyl chloride monomer as well as a resin composed of a vinyl chloride monomer and copolymerizable with the vinyl chloride monomer (the content of the vinyl chloride monomer in the total composition of the resin 50 wt% or more).
- Vinyl monomers copolymerizable with such vinyl chloride monomers include olefin compounds such as ethylene and propylene; Unsaturated nitriles such as vinyl esters such as vinyl acetate and vinyl propionate and acrylonitrile; Vinyl alkyl ethers such as vinyl methyl ether and vinyl ethyl ether; Unsaturated fatty acids such as acrylic acid, methacrylic acid itaconic acid and maleic acid; And anhydrides of these fatty acids; may be used alone or in combination of two or more selected from the group consisting of.
- BND t-butyl peroxyneodecanoate
- the polymerization temperature is continuously controlled by 0.2 ° C / min by controlling the temperature using steam or cooling water of a specific temperature. Increasing pressure to maintain pressure. After the temperature was raised for about 35 minutes, the temperature was stopped and when the pressure reached 7.0 kgf / cm 2 , the reactor was cooled down and stopped by adding 0.02 parts by weight of Irganox 245 and 0.01 parts by weight of sodium bicarbonate as an antioxidant. Unreacted vinyl chloride monomer was recovered through devacuum and the vinyl chloride resin slurry was recovered.
- the resulting slurry was washed and dried to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.4 ⁇ ⁇ from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.6 ° C from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.05 ° C from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased when the pressure reduction degree at the end of the reaction was 0.05 kgf / cm 2 , thereby obtaining a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased when the pressure reduction degree at the end of the reaction was 0.15 kgf / cm 2 , thereby obtaining a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 30 minutes after the end of the pressure drop occurred, thereby obtaining a vinyl chloride resin having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 50 minutes after the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin having a number average degree of polymerization of 1000.
- Example 2 In order to compare with the vinyl chloride resin production method of Example 1, the same method was repeated except that the polymerization temperature was not increased even after the pressure drop occurred at the end of the reaction in Example 1, to obtain a vinyl chloride resin having a number average degree of polymerization of 1000. Prepared.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.008 ° C from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.8 ° C at the end of the reaction at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 except that the degree of pressure drop at the end of the reaction was 0.01 kgf / cm 2 , the polymerization was repeated under the same conditions as in Example 1 to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the degree of pressure drop at the end of the reaction was 0.5 kgf / cm 2 to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 10 minutes after the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 90 minutes after the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin having a number average degree of polymerization of 1000.
- Example 1 the polymerization was repeated under the same conditions as in Example 1 except that after the pressure drop occurred at the end of the reaction, the inlet of the cooling water was stopped in the jacket to raise the temperature of the polymerization reactor contents from 58 ° C to 70 ° C irregularly. A vinyl chloride resin having an average degree of polymerization of 1000 was obtained.
- Residual initiator concentration measurement was used to measure the content of residual initiator present in the produced vinyl chloride resin. That is, 50 parts by weight of the prepared resin, 80 parts by weight of isopropyl alcohol (IPA) was mixed, and 20 ml of 10% acetic acid solution and 20 ml of 10% potassium iodide solution were mixed and sufficiently mixed.
- IPA isopropyl alcohol
- Particle size distribution measurement The obtained resin was measured for particle size using Sumpatec's HELOS particle size analyzer, and the span value at that time was defined as the particle size distribution. In this case, the lower the span value, the smaller the deviation.
- Example 2 Example 3
- Example 4 Example 5
- Example 6 Example 7
- Example 8 Temperature rise rate (°C / min) 0.2 0.4 0.6 0.05 0.2 0.2 0.2 0.2 Pressure drop ( ⁇ P, kgf / cm 2 ) 0.1 0.1 0.1 0.1 0.05 0.15 0.1 0.1 Temperature rise time (minutes) 35 35 35 35 35 35 30 50
- Whiteness 75
- 76 75
- 74 75
- 74 73 Residual initiator concentration
- ppm 10 8 5 12 7 11 14 4 Whiskey (number) 5 5 4 5 4 7 6 6
- the whiteness and the polymerization time may be controlled, thereby improving the whiteness and the whiskey.
- the pressure drop was prevented by raising the temperature above the polymerization temperature using a temperature control system according to the degree of pressure drop at the end of the reaction at which the pressure drop occurred, and the pressure drop at the end of the reaction and the high heat removal amount of the reflux condenser By suppressing the foam generated, it was possible to efficiently produce a whiskey and a high vinyl chloride-based resin.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a method for preparing a vinyl-based polymer and a vinyl-based copolymer including a vinyl chloride-based material through suspension polymerization in which the generation of foam is prevented while maintaining the pressure by slowly increasing the reaction temperature when the pressure starts to drop at a reaction terminal stage. In the method for preparing a vinyl-based resin, a vinyl chloride-based monomer is suspension polymerized to reduce the generation of foam and improve the quality of protrusions, thermal stability and the like.
Description
본 발명은 염화비닐계 수지의 제조방법에 관한 것으로, 더욱 상세하게는 염화비닐계 수지 제조시 반응 후반에서 압력이 떨어지는 시점에 중합 온도를 분당 소정 온도씩 서서히 승온시켜 압력 저하 및 폼 발생을 방지함으로써 돌기 품질을 개선하고 잔류 개시제에 의한 열안정성을 해결하여 품질을 개선하는 염화비닐계 수지의 제조방법에 관한 것이다.The present invention relates to a method for producing a vinyl chloride-based resin, and more particularly, by gradually increasing the polymerization temperature by a predetermined temperature per minute at the time of the pressure drop in the second half of the reaction during the production of the vinyl chloride-based resin to prevent pressure drop and foam generation. It relates to a method for producing a vinyl chloride-based resin to improve the quality of the projections and to improve the quality by solving the thermal stability of the residual initiator.
염화비닐계 수지는 가격이 저렴하며 우수한 가공성, 내화학성, 내구성, 절연성 등의 성질을 가지고 있어 경질과 연질의 재료로서 파이프, 벽지, 창틀, 전선 피복, 랩 필름, 시트 등 범용적으로 사용되고 있다. 하지만 염화비닐계 수지가 널리 이용되어 성형 가공에 대한 고객의 눈높이가 높아지면서 성형 가공성에 대한 개선이 지속적으로 요구되고 있다.Vinyl chloride-based resins are inexpensive and have excellent processability, chemical resistance, durability, insulation properties, and are widely used as hard and soft materials such as pipes, wallpaper, window frames, wire coatings, wrap films, and sheets. However, as vinyl chloride-based resins are widely used, customer's eye level on molding processing has been increased, and improvement of molding processability is continuously required.
일반적으로 염화비닐계 수지의 가공성은 입자의 내부 공극률, 입경, 입자 분포 및 모폴로지의 영향을 받으며 이를 조절함으로써 수지의 용융성을 높이고자 한다. 이러한 수지의 용융 특성을 평가하는 품질 기준 중 하나는 돌기 또는 휘시-아이(Fish-Eye)라 불리는데, 이것의 발생 정도로 용융 정도의 차이 및 최종 제품의 품질을 확인할 수 있다.In general, the processability of the vinyl chloride-based resin is affected by the internal porosity, particle diameter, particle distribution, and morphology of the particles and is intended to increase the meltability of the resin. One of the quality criteria for evaluating the melting characteristics of these resins is called protrusions or fish-eyes, which can confirm the difference in the degree of melting and the quality of the final product.
이러한 돌기 품질 저하의 원인으로 입자들의 용융성 차이가 의심되며, 이러한 미용융 입자들의 생성은 반응 중 발생하는 폼과 연관 지을 수 있다. 자세하게 살펴보면, 반응 말기 환류 응축기의 높은 사용량과 압력 저하 시점과 교차하면서 폼이 발생하게 되는데, 입자가 포함된 드라이 폼은 반응기 상부 및 환류 응축기로 부상하게 된다. 하지만 배치마다 충분한 클리닝이 어렵기 때문에 폼에 의해 부상한 입자들이 반응기 및 환류응축기 내부에 남아 다음 반응에 포함되면서 재중합을 거치게 되어 크고, 내부 공극률이 낮은 입자를 생성하게 된다. 이렇게 용융성이 낮은 입자의 생성은 돌기 품질을 악화시키게 된다.The difference in the meltability of the particles is suspected as a cause of the deterioration of the protrusion quality, and the production of such unmelted particles may be associated with the foam generated during the reaction. In detail, foam is generated by crossing the high usage and pressure drop of the reflux condenser at the end of the reaction, and the dry foam containing the particles floats to the top of the reactor and to the reflux condenser. However, due to the difficulty of sufficient cleaning in each batch, the particles floated by the foam remain inside the reactor and the reflux condenser, and are subjected to repolymerization as they are included in the next reaction to generate large, low internal porosity particles. The production of particles of low meltability deteriorates the projection quality.
이와 같은 문제를 해결하기 위한 종래 기술로는 미국특허 제5,087,678호와 일본공개특허 제2007-284510호에서 살펴보면 알 수 있듯이 반응 중 폼 발생을 억제 하기 위한 방법으로 소포제를 단독 사용하거나 소포제를 다른 첨가제와 혼합하여 폼의 발생을 억제하고자 하는 방법이 사용되어 왔다. 하지만 소포제 단독 사용으로는 드라이 폼 발생을 억제하기가 어렵고, 반응 중 소포제 및 첨가제를 추가 투입하기 위해서는 설비 투자와 소포제 및 첨가제의 투입되는 양에 대한 가격 등 경제적으로 문제점이 있으며 소포제 투입에 따라 품질이 저하되는 문제점이 있다.As a conventional technique for solving such a problem, as can be seen in US Patent No. 5,087,678 and Japanese Patent Application Laid-Open No. 2007-284510, a method for inhibiting foam generation during a reaction may be used alone or by using an antifoaming agent with other additives. Methods have been used to suppress the occurrence of foam by mixing. However, it is difficult to suppress the occurrence of dry foam by using antifoaming agent alone.In order to add antifoaming agents and additives during the reaction, there are economic problems such as investment in equipment and the price of the amount of antifoaming agent and additives added. There is a problem of deterioration.
본 발명의 목적은 상기 종래기술의 문제점을 해결하기 위한 것으로서, 본 발명은 반응 말기 압력 저하가 발생하는 시점에 중합 온도를 기준 온도에서 분당 소정 온도씩 승온시켜 압력 저하 및 폼 발생을 방지하여 재중합 및 스케일 생성을 방지하고자 한다.An object of the present invention is to solve the problems of the prior art, the present invention is to increase the polymerization temperature by a predetermined temperature per minute from the reference temperature at the time when the pressure drop occurs at the end of the reaction to prevent the pressure drop and foam generation repolymerization And scale generation.
또한, 본 발명은 높아진 온도에 의해 개시제의 분해를 유도함으로써 반응 종료 후 잔류하는 개시제의 함량을 낮춰 돌기 발생이 적고 열 안정성이 우수한 염화비닐계 수지를 제조하여 기존의 방법이 가지는 스케일 발생의 문제나 돌기, 열 안정성에 의한 품질 문제가 없는 수지의 제조방법을 제공하고자 한다.In addition, the present invention induces decomposition of the initiator by the elevated temperature to lower the content of the initiator remaining after the end of the reaction to produce a vinyl chloride-based resin with less projections and excellent thermal stability, so the problem of scale generation of the existing method An object of the present invention is to provide a method for producing a resin without quality problems due to protrusions and thermal stability.
본 발명의 상기 목적 및 다른 목적은 하기 설명되는 본 발명에 의하여 모두 달성 될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
상기 본 발명의 목적을 달성하기 위하여, 본 발명은 현탁 중합에 의한 염화비닐계 수지의 제조방법에 있어서, 반응 말기에 압력이 저하되는 시점부터 중합 온도를 승온시키는 것을 특징으로 하는 염화비닐계 수지의 제조방법을 제공한다.In order to achieve the object of the present invention, the present invention is a method for producing a vinyl chloride resin by suspension polymerization, the polymerization temperature of the vinyl chloride resin, characterized in that to increase the temperature from the time point at which the pressure is reduced at the end of the reaction It provides a manufacturing method.
또한 본 발명은 현탁 중합 반응 개시 이후에 반응압력이 0.01 kgf/cm2 초과 내지 0.5 kgf/cm2 미만 저하되는 시점부터, 0.008 ℃/min 초과 내지 0.8 ℃/min 미만의 승온속도로, 10분 초과 내지 90분 미만 동안 승온하는 것을 특징으로 하는 염화비닐계 수지의 제조방법을 제공한다.In addition, the present invention after the start of the suspension polymerization reaction from the time when the reaction pressure is lowered more than 0.01 kgf / cm 2 to less than 0.5 kgf / cm 2 , at a temperature rising rate of more than 0.008 ℃ / min to less than 0.8 ℃ / min, more than 10 minutes It provides a method for producing a vinyl chloride-based resin, characterized in that to increase the temperature for less than 90 minutes.
상기 저하되는 반응압력은 일례로 0.01 kgf/cm2 초과 내지 0.2 kgf/cm2 미만인 것을 특징으로 한다. The decreasing reaction pressure is characterized in that more than 0.01 kgf / cm 2 to less than 0.2 kgf / cm 2 as an example.
상기 승온속도는 일례로 0.008 ℃/min 초과 내지 0.65 미만 ℃/min인 것을 특징으로 한다. The temperature increase rate is, for example, characterized in that more than 0.008 ℃ / min less than 0.65 ℃ / min.
상기 승온속도는 일례로 온도제어시스템을 조절하는 것을 특징으로 한다.The temperature increase rate is characterized by adjusting the temperature control system as an example.
상기 중합의 반응 온도는 일례로 30 내지 80℃ 범위 내인 것을 특징으로 한다.The reaction temperature of the polymerization is characterized in that within 30 to 80 ℃ range, for example.
상기 승온 시간은 일례로 30 내지 60분인 것을 특징으로 한다.The temperature increase time is, for example, characterized in that 30 to 60 minutes.
또한 본 발명은 상기 염화비닐계 수지의 제조방법에 의하여 제조되는 염화비닐계 수지를 제공한다.In another aspect, the present invention provides a vinyl chloride-based resin prepared by the method for producing a vinyl chloride-based resin.
상기 염화비닐계 수지는 일례로 잔류 개시제 농도가 염화비닐계 수지 100 중량부를 기준으로 0.002 중량부 미만인 것을 특징으로 한다.The vinyl chloride-based resin, for example, is characterized in that the residual initiator concentration is less than 0.002 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.
또한 본 발명은 상기 염화비닐계 수지, 무기충진제 및 안정화제를 포함하는 염화비닐계 수지 조성물을 제공한다.In another aspect, the present invention provides a vinyl chloride-based resin composition comprising the vinyl chloride-based resin, inorganic filler and stabilizer.
상기 무기충진제는 일례로 카본블랙인 것을 특징으로 한다.The inorganic filler is characterized in that the carbon black as an example.
상기 염화비닐계 수지 조성물은 휘시-아이 개수(두께 0.3 mm, 면적 400 cm2)가 10개 미만인 것을 특징으로 한다.The vinyl chloride-based resin composition is characterized in that the number of fish-eyes (thickness 0.3 mm, area 400 cm 2 ) is less than 10.
또한, 본 발명은 현탁 중합 반응 개시 이후에 반응압력이 0.05 내지 0.1 kgf/cm2 저하되는 시점부터, 0.01 내지 0.5 ℃/min의 승온속도로 20 내지 60분 동안 승온하는 것을 특징으로 하는 염화비닐계 수지의 제조방법을 제공한다. In addition, the present invention is a vinyl chloride system, characterized in that the temperature rises for 20 to 60 minutes at a temperature increase rate of 0.01 to 0.5 ℃ / min from the time when the reaction pressure is lowered from 0.05 to 0.1 kgf / cm 2 after starting the suspension polymerization reaction It provides a method for producing a resin.
상기에서 살펴본 바와 같이, 본 발명의 방법에 따르면 현탁 중합에 의해 염화비닐계 수지를 제조하는 단계에서 중합 온도 별로 승온 속도를 조절하며 반응 말기 압력 저하를 방지할 수 있으며, 이에 말기에 증가하는 환류 응축기 제열 시점과 겹치게 되면서 나타나는 폼 발생을 억제하는 이점을 갖는다. 또한, 종래의 스케일 문제와 재중합 문제에 따른 돌기 품질 및 열안정성 문제점을 해결할 수 있다.As described above, according to the method of the present invention, in the step of preparing the vinyl chloride-based resin by suspension polymerization, it is possible to control the temperature increase rate for each polymerization temperature and to prevent the pressure drop at the end of the reaction, thereby increasing the reflux condenser. It has the advantage of suppressing the foam generation appearing while overlapping the heat removal point. In addition, it is possible to solve the problem of protrusion quality and thermal stability due to the conventional scale problem and repolymerization problem.
본 발명에서는 종래의 기술이 갖는 단점을 해결하기 위하여 반응 말기 압력 저하가 발생하는 시점에 온도를 서서히 승온시켜 압력 저하를 방지하여 환류 응축기의 높은 사용량과 압력 저하의 교차 시점에 발생할 수 있는 폼의 가능성을 제거하고, 반응 말기 잔류하고 있는 개시제의 분해를 유도하여 반응 후 품질이 개선되는 수지를 제조하는 방법을 제공한다.In the present invention, in order to solve the disadvantages of the prior art, by raising the temperature gradually at the time of the end of the pressure drop occurs to prevent the pressure drop, the possibility of foam that can occur at the time of the intersection of the high amount of reflux condenser and the pressure drop It provides a method for producing a resin that is removed, and induces decomposition of the initiator remaining at the end of the reaction to improve the quality after the reaction.
본 발명은 반응 후 폼이 발생하지 않아 다음 반응에 재중합 가능한 입자의 유입을 방지하고, 잔류 개시제가 남지 않아 열안정성이 동시에 향상되도록 하여 품질의 개선이 가능하다.In the present invention, foam does not occur after the reaction to prevent the inflow of particles that can be repolymerized in the next reaction, and the residual initiator is not left so that the thermal stability is simultaneously improved, thereby improving quality.
본 발명에 따르면, 중합도 별로 다른 중합 온도와 다른 중합 개시제를 투입하면서 현탁 중합에 의해 염화비닐계 수지를 제조하는 방법에 있어서 반응 중 발생하는 폼 발생을 최소화하고 잔류 개시제의 함량을 최소화하기 위해 반응 말기 중합 온도를 기준 온도보다 분당 소정 온도씩 승온시켜 반응 말기에 나타나는 압력 저하를 방지하여 폼의 발생을 조절하는 것을 특징으로 하는 염화비닐계 수지의 제조방법을 제공한다.According to the present invention, in the method for producing a vinyl chloride-based resin by suspension polymerization while adding different polymerization temperatures and different polymerization initiators according to the degree of polymerization, in order to minimize the generation of foam generated during the reaction and to minimize the content of the residual initiator It provides a method of producing a vinyl chloride-based resin, characterized in that the polymerization temperature is raised by a predetermined temperature per minute to prevent the pressure drop appearing at the end of the reaction to control the generation of foam.
이하에서 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에서는 종래 기술의 반응 말기에 환류 응축기에 의한 제열량이 높아지고 중합 전환율이 높아지면서 반응 말기 압력 저하 시점과 교차하여 입자를 포함한 드라이 폼이 발생하고 이러한 폼에 의해 반응기 상부 및 환류 응축기 내에 스케일 및 재중합이 발생하는 문제점을 해결하고, 잔류 개시제의 높은 수준을 해결함으로써 품질 개선에 대한 어려움을 극복할 수 있는 새로운 염화비닐계 수지의 제조방법을 제공하는 것을 기술적 특징으로 한다.In the present invention, the amount of defrosting by the reflux condenser is increased at the end of the reaction of the prior art and the polymerization conversion rate is increased, and a dry foam containing particles is generated at the end of the pressure drop at the end of the reaction. It is a technical feature to provide a new method for producing a vinyl chloride-based resin that can overcome the problems of quality improvement by solving the problem that repolymerization occurs, and solve the high level of residual initiator.
상술한 기술적 특징을 달성하기 위해, 반응 말기에 압력이 저하되는 시점에 반응 온도를 분당 0.008℃ 초과 내지 0.8℃ 미만씩 서서히 승온시켜 반응기 내 정해진 제열 한계를 초과하지 않도록 하면서 압력 저하가 일어나는 것을 조절하여 압력 변화에 따른 폼 발생을 방지함으로써 얻어진 최종 수지의 용융성이 개선될 수 있도록 한다. 바람직하게는 0.01℃ 내지 0.65℃ 미만 또는 0.02℃ 내지 0.65℃씩, 더욱 바람직하게는 0.05℃ 내지 0.6℃씩 승온할 수 있다. 반응 말기에 압려겨이 저하되는 시점에 승온 속도를 분당 상기 온도 범위를 초과하여 조절할 경우에는 급격하게 온도가 증가되어 압력 및 반응 안정성이 흐트러지면서 품질에도 악영향을 끼치게 된다. 반면에 승온 속도를 상기 온도 범위 미만으로 할 경우 승온이 느리게 되어 압력 저하를 방지하지 못하게 되어 종래 기술의 문제점이 똑같이 나타나게 된다.In order to achieve the above technical features, at the end of the reaction at the time when the pressure is lowered by gradually raising the reaction temperature by more than 0.008 ℃ to less than 0.8 ℃ per minute to control the pressure drop occurs while not exceeding the defined defrost limit in the reactor by By preventing foam generation due to pressure change, the meltability of the final resin obtained can be improved. Preferably it can raise a temperature below 0.01 degreeC-0.65 degreeC or 0.02 degreeC-0.65 degreeC, More preferably, 0.05 degreeC-0.6 degreeC. When the temperature increase rate is adjusted beyond the temperature range per minute at the time when the pressure is lowered at the end of the reaction, the temperature is rapidly increased, which adversely affects the quality while disturbing the pressure and the stability of the reaction. On the other hand, if the temperature increase rate is lower than the above temperature range, the temperature rise becomes slow and the pressure drop cannot be prevented, so that the problems of the prior art appear in the same manner.
본 발명에서 설명하는 반응 말기 발생하는 압력 저하 시점에서 온도를 승온시키는 시점은 압력 저하가 0.01kgf/cm2 초과 내지 0.5kgf/cm2 미만 정도 나타나는 시점으로 한다. 바람직하게는 0.05에서 0.2kgf/cm2 미만의 압력 저하 시점에서 승온시키는 것이다. 상기 범위의 압력 저하가 나타나기 전에 승온시키면 상승한 온도에 대해 압력 변화가 발생하여 불안정하게 되어 품질 문제가 발생할 수 있으며, 압력 저하가 상기 범위를 초과한 후 승온시키면 이미 환류 응축기의 제열량과 압력 저하로 입자를 포함한 폼이 발생하게 되기 때문에 이에 의해 돌기 및 반응기 내부 스케일을 발생시켜 악영향을 끼치게 된다. The present invention the time for raising the temperature at the time of pressure decrease caused the reaction end is described in the time shown is about 0.01kgf / cm 2 to less than 0.5kgf / cm 2 the pressure drop. Preferably, the temperature is increased at a pressure drop time of 0.05 to less than 0.2 kgf / cm 2 . If the temperature is raised before the pressure drop in the above range, a pressure change may occur to the elevated temperature, resulting in unstable quality problems, and if the temperature is increased after the pressure drop exceeds the above range, the heat removal amount and the pressure drop of the reflux condenser are Since foam containing particles is generated, this causes protrusions and internal scales of the reactor, which adversely affects it.
상기의 중합 온도는 일반적으로 수지의 중합도에 의해 결정되는데, 일반적으로 적용되는 온도는 수 평균 중합도 1000 제품의 경우 55 내지 60℃, 수 평균 중합도 800 제품의 경우 61 내지 65℃, 수 평균 중합도 700 제품의 경우 66 내지 70℃의 범위에서 결정된다.The polymerization temperature is generally determined by the degree of polymerization of the resin, and the temperature generally applied is 55 to 60 ° C. for the number average degree of polymerization of 1000 products, 61 to 65 ° C. for the number average degree of polymerization of 800 products and 700 number average degree of polymerization of the products. In the case of it is determined in the range of 66 to 70 ℃.
본 발명에서의 중합 온도는 30 내지 80℃ 범위 내를 만족하는 것이 바람직하다. 더욱 바람직한 중합 기준 온도는 40 내지 70℃ 범위 내를 만족하고, 더욱더 바람직하게는 50 내지 65℃ 범위를 만족하도록 한다.It is preferable that the polymerization temperature in this invention satisfy | fills the range of 30-80 degreeC. More preferred polymerization reference temperatures are within the range from 40 to 70 ° C, even more preferably from 50 to 65 ° C.
중합도란 고분자를 구성하는 반복된 단위, 즉 단위체 또는 단량체의 수를 말하며, 본 발명에서는 수평균 중합도를 사용한다.The degree of polymerization refers to the number of repeated units, ie units or monomers, constituting the polymer, and the number average degree of polymerization is used in the present invention.
상기의 중합 온도에 따라 반응 압력도 달라지기 때문에 압력 저하되는 정도도 차이가 나타난다. 이에 중합 온도에 따라 반응 말기 압력이 저하되는 차이에 따라 승온 속도를 조절할 수 있도록 하며 이에 반응 안정성에 무리를 갖지 않도록 하여 반응할 수 있도록 한다.Since the reaction pressure also varies depending on the polymerization temperature, the degree to which the pressure falls is also different. Accordingly, it is possible to control the temperature increase rate according to the difference in the pressure decreases at the end of the reaction according to the polymerization temperature, so that the reaction stability does not have a burden on the reaction stability.
추가적으로 압력 저하가 발생하여 기존의 중합 온도에서 승온시키는 시간은 압력 저하가 발생한 이후부터 30분 내지 60분, 바람직하게는 30분 내지 50분, 더욱더 바람직하게는 30분 내지 40분 동안 진행한다.In addition, the pressure drop occurs to increase the temperature at the existing polymerization temperature for 30 minutes to 60 minutes, preferably 30 minutes to 50 minutes, even more preferably 30 minutes to 40 minutes after the pressure drop occurs.
이는 전체 중합시간에 크게 영향을 주지 않도록 하며 반응 종료시까지 진행하는 것으로 한다. 승온시키는 시간이 너무 짧으면 승온이 중지된 이후 압력 저하가 급격하게 일어나면서 폼 발생 가능성이 높아질 수 있어 돌기 및 반응기 내 스케일이 발생하는 문제가 있다. 또한 승온시키는 시간이 너무 길어지면 입자 내부 모폴로지에 영향을 끼칠 수 있고, 중합시간이 너무 길어져 단위시간당 생산량이 감소하는 단점을 갖는다. 추가적으로 중합 온도를 승온함에 따라 승온시키는 최대 온도 범위는 앞에 제시한 중합 온도 범위인 30℃ 내지 80℃를 벗어나지 않도록 한다.This does not significantly affect the overall polymerization time and is to proceed until the end of the reaction. If the temperature increase time is too short, the pressure drop may occur rapidly after the temperature stops, and the possibility of foam generation may increase, thereby causing protrusion and scale in the reactor. In addition, if the time to increase the temperature too long may affect the internal morphology of the particles, the polymerization time is too long has the disadvantage that the output per unit time decreases. Additionally, as the polymerization temperature is raised, the maximum temperature range for raising the temperature does not deviate from the above-mentioned polymerization temperature range of 30 ° C to 80 ° C.
상기의 중합에서 적절한 개시제는 다음과 같다.Suitable initiators in the above polymerizations are as follows.
α,α'-비스(네오테카노일 퍼옥시)디이소프로필 벤젠, 큐멘 퍼옥시네오데카노에이트, 디-n-프로필 퍼옥시 디카보네이트, 디이소프로필 퍼옥시 디카보네이트, 1,1,3,3-테트라메틸부틸 퍼옥시 네오데카노에이트, 비스(4-t-부틸사이클로헥실) 퍼옥시 디카보네이트, 1-사이클로헥실-1-메틸에틸 퍼옥시네오데카노에이트, 디-2-에톡시에틸 퍼옥시 디카보네이트, 디-2-에틸헥실 퍼옥시 디카보네이트, t-헥실 퍼옥시네오데카노에이트, 디메톡시부틸 퍼옥시 디카보네이트, 비스(3-메틸-3-메톡시부틸)퍼옥시 디카보네이트, t-부틸 퍼옥시네오데카노에이트, t-헥실 퍼옥시피발레이트 등의 퍼옥사이드류와 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(이소부티로니트릴), 디메틸 2.2'-아조비스(이소부티레이트)등의 아조 화합물로부터 선택된 1종 이상이 사용될 수 있으나, 이에 한정되는 것은 아니다.α, α'-bis (neotecanoyl peroxy) diisopropyl benzene, cumene peroxyneodecanoate, di-n-propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, 1,1,3 , 3-tetramethylbutyl peroxy neodecanoate, bis (4-t-butylcyclohexyl) peroxy dicarbonate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2-ethoxy Ethyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, t-hexyl peroxy neodecanoate, dimethoxybutyl peroxy dicarbonate, bis (3-methyl-3-methoxybutyl) peroxy di Peroxides such as carbonate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (Isobutyronitrile), one or more selected from azo compounds such as dimethyl 2.2'-azobis (isobutyrate) may be used. I, and the like.
반응기에 주입하는 중합 개시제의 양은 종래의 중합시 사용되는 중합 개시제와 동량으로 투입되는 것을 특징으로 하며, 이에 따라 염화비닐계 단량체 100 중량부에 대하여 0.02 내지 0.3 중량부, 혹은 0.03 내지 0.2 중량부 또 다른 일례로 0.04 내지 0.15 중량부의 사용이 적절하다.The amount of the polymerization initiator to be injected into the reactor is characterized in that the same amount as the polymerization initiator used in the conventional polymerization, it is characterized in that 0.02 to 0.3 parts by weight, or 0.03 to 0.2 parts by weight based on 100 parts by weight of the vinyl chloride monomer As another example, use of 0.04 to 0.15 parts by weight is appropriate.
본 발명은 상기와 같은 염화비닐계 수지의 제조방법에 의하여 제조됨을 특징으로 하는 염화비닐계 수지를 제공한다.The present invention provides a vinyl chloride-based resin, characterized in that it is prepared by the method for producing a vinyl chloride-based resin as described above.
상기 염화비닐계 수지는, 잔류 개시제 농도가 염화비닐계 수지 100 중량부를 기준으로 0.002 중량부 미만, 혹은 0.0005 내지 0.0015 중량부, 더욱 바람직하게는 0.0006 내지 0.001 중량부가 적절하다.The vinyl chloride-based resin has a residual initiator concentration of less than 0.002 parts by weight, or 0.0005 to 0.0015 parts by weight, more preferably 0.0006 to 0.001 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.
참고로, 본 발명의 염화비닐계 수지는 순수하게 염화비닐 단량체로 이루어진 수지뿐 아니라 염화비닐 단량체를 주체로 하고 이것과 공중합 가능한 비닐계 단량체와의 공중합체(수지 전체 조성 중 염화비닐 단량체의 함량이 50 중량% 이상)도 포함된다.For reference, the vinyl chloride-based resin of the present invention is a copolymer of a vinyl chloride monomer composed mainly of a vinyl chloride monomer as well as a resin composed of a vinyl chloride monomer and copolymerizable with the vinyl chloride monomer (the content of the vinyl chloride monomer in the total composition of the resin 50 wt% or more).
이 같은 염화비닐 단량체와 공중합가능한 비닐계 단량체로는 에틸렌, 프로필렌 등의 올레핀 화합물; 초산 비닐, 포로피온산 비닐 등의 비닐 에스테르류, 아크릴로니트릴 등의 불포화 니트릴류; 비닐 메틸 에테르, 비닐 에틸 에테르 등의 비닐 알킬 에테르류; 아크릴산, 메타크릴산 이타콘산, 말레인산 등의 불포화 지방산; 및 이들 지방산의 무수물;로 이루어진 군으로부터 선택된 1종 또는 2종 이상 혼합하여 사용할 수 있다.Vinyl monomers copolymerizable with such vinyl chloride monomers include olefin compounds such as ethylene and propylene; Unsaturated nitriles such as vinyl esters such as vinyl acetate and vinyl propionate and acrylonitrile; Vinyl alkyl ethers such as vinyl methyl ether and vinyl ethyl ether; Unsaturated fatty acids such as acrylic acid, methacrylic acid itaconic acid and maleic acid; And anhydrides of these fatty acids; may be used alone or in combination of two or more selected from the group consisting of.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. Naturally, changes and modifications belong to the appended claims.
[실시예]EXAMPLE
실시예 1Example 1
1입방 미터 크기의 반응기에 염화비닐 단량체 100 중량부, 탈이온수 130 중량부, 검화도 72%인 폴리비닐 분산제 0.04 중량부, 55% 폴리비닐 분산제 0.02 중량부를 투입하였다.100 parts by weight of a vinyl chloride monomer, 130 parts by weight of deionized water, 0.04 part by weight of a polyvinyl dispersant having a degree of saponification of 72%, and 0.02 part by weight of a 55% polyvinyl dispersant were introduced into a 1 cubic meter reactor.
중합 개시제로 t-부틸 퍼옥시네오데카노에이트 (t-butyl peroxyneodecanoate, BND)를 0.02 중량부를 넣고 반응기를 탈압력화하여 교반하면서 공기와 질소를 제거하였다.As the polymerization initiator, 0.02 parts by weight of t-butyl peroxyneodecanoate (BND) was added thereto, and the reactor was depressurized to remove air and nitrogen.
이를 가열하여 목표로 하는 중합 온도 58℃로 유지시키고 반응 말기 반응기 내부 압력이 0.1kgf/cm2 정도 떨어질 때, 중합 온도를 스팀이나 특정 온도의 냉각수를 이용하여 온도를 제어함으로써 연속적으로 분당 0.2℃씩 증가시켜 압력을 유지시켰다. 약 35분 동안 승온시킨 후에 승온을 멈추고 압력이 7.0kgf/cm2에 도달하면 반응기를 냉각시키고 산화방지제로 Irganox 245 0.02 중량부 및 탄산수소나트륨 0.01 중량부를 첨가하여 정지시켰다. 탈진공을 통해 미반응 염화비닐 단량체를 회수하고 염화비닐 수지 슬러리를 회수하였다.It is heated to maintain the target polymerization temperature of 58 ° C, and when the pressure in the reactor at the end of the reaction drops by about 0.1kgf / cm 2 , the polymerization temperature is continuously controlled by 0.2 ° C / min by controlling the temperature using steam or cooling water of a specific temperature. Increasing pressure to maintain pressure. After the temperature was raised for about 35 minutes, the temperature was stopped and when the pressure reached 7.0 kgf / cm 2 , the reactor was cooled down and stopped by adding 0.02 parts by weight of Irganox 245 and 0.01 parts by weight of sodium bicarbonate as an antioxidant. Unreacted vinyl chloride monomer was recovered through devacuum and the vinyl chloride resin slurry was recovered.
얻어진 슬러리를 세척 및 건조하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다.The resulting slurry was washed and dried to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
실시예 2Example 2
실시예 1에서 반응 말기 압력 저하가 발생하는 시점부터 중합 온도를 0.4℃씩 승온시키는 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다.In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.4 占 폚 from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
실시예 3Example 3
실시예 1에서 반응 말기 압력 저하가 발생하는 시점부터 중합 온도를 0.6℃씩 승온시키는 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.6 ° C from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
실시예 4Example 4
실시예 1에서 반응 말기 압력 저하가 발생하는 시점부터 중합 온도를 0.05℃씩 승온시키는 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다.In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.05 ° C from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
실시예 5Example 5
실시예 1에서 반응 말기 압력 저하 정도가 0.05kgf/cm2일 때 중합온도를 증가시킨 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다.In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased when the pressure reduction degree at the end of the reaction was 0.05 kgf / cm 2 , thereby obtaining a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
실시예 6 Example 6
실시예 1에서 반응 말기 압력 저하 정도가 0.15kgf/cm2일 때 중합온도를 증가시킨 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다.In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased when the pressure reduction degree at the end of the reaction was 0.15 kgf / cm 2 , thereby obtaining a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
실시예 7Example 7
실시예 1에서 반응 말기 압력 저하가 발생한 이후 승온을 30분 동안 진행한 것을 제외하고는 실시예 1과 동일 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐계 수지를 수득하였다.In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 30 minutes after the end of the pressure drop occurred, thereby obtaining a vinyl chloride resin having a number average degree of polymerization of 1000.
실시예 8Example 8
실시예 1에서 반응 말기 압력 저하가 발생한 이후 승온을 50분 동안 진행한 것을 제외하고는 실시예 1과 동일 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐계 수지를 수득하였다In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 50 minutes after the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin having a number average degree of polymerization of 1000.
비교예 1Comparative Example 1
실시예 1의 염화비닐 수지 제조방법과 비교하기 위하여, 실시예 1에서 반응 말기 압력 저하가 발생한 후에도 중합 온도를 승온시키지 않은 것을 제외하고는 동일한 방법을 반복하여 수평균 중합도 1000의 염화비닐계 수지를 제조하였다.In order to compare with the vinyl chloride resin production method of Example 1, the same method was repeated except that the polymerization temperature was not increased even after the pressure drop occurred at the end of the reaction in Example 1, to obtain a vinyl chloride resin having a number average degree of polymerization of 1000. Prepared.
비교예 2Comparative Example 2
실시예 1에서 반응 말기 압력 저하가 발생하는 시점부터 중합 온도를 0.008℃씩 승온시킨 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다. In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.008 ° C from the time when the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
비교예 3Comparative Example 3
실시예 1에서 반응 말기 압력 저하가 발생하는 시점부터 중합 온도를 0.8℃씩 승온시키는 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다. In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the polymerization temperature was increased by 0.8 ° C at the end of the reaction at the end of the reaction to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
비교예 4Comparative Example 4
실시예 1에서 반응 말기 압력 저하 정도가 0.01kgf/cm2인 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다.In Example 1, except that the degree of pressure drop at the end of the reaction was 0.01 kgf / cm 2 , the polymerization was repeated under the same conditions as in Example 1 to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
비교예 5Comparative Example 5
실시예 1에서 반응 말기 압력 저하 정도가 0.5kgf/cm2인 것을 제외하고는 실시예 1과 동일한 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐 수지 중합체를 수득하였다.In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the degree of pressure drop at the end of the reaction was 0.5 kgf / cm 2 to obtain a vinyl chloride resin polymer having a number average degree of polymerization of 1000.
비교예 6Comparative Example 6
실시예 1에서 반응 말기 압력 저하가 발생한 이후 승온을 10분 동안 진행한 것을 제외하고는 실시예 1과 동일 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐계 수지를 수득하였다. In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 10 minutes after the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin having a number average degree of polymerization of 1000.
비교예 7Comparative Example 7
실시예 1에서 반응 말기 압력 저하가 발생한 이후 승온을 90분 동안 진행한 것을 제외하고는 실시예 1과 동일 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐계 수지를 수득하였다. In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that the temperature was increased for 90 minutes after the pressure drop occurred at the end of the reaction to obtain a vinyl chloride resin having a number average degree of polymerization of 1000.
비교예 8Comparative Example 8
실시예 1에서 반응 말기 압력 저하가 발생한 이후 자켓에 냉각수 유입을 정지시켜 중합반응기 내용물의 온도를 58℃에서 불규칙하게 70℃까지 승온시킨 것을 제외하고는 실시예 1과 동일 조건으로 중합을 반복하여 수평균 중합도 1000의 염화비닐계 수지를 수득하였다. In Example 1, the polymerization was repeated under the same conditions as in Example 1 except that after the pressure drop occurred at the end of the reaction, the inlet of the cooling water was stopped in the jacket to raise the temperature of the polymerization reactor contents from 58 ° C to 70 ° C irregularly. A vinyl chloride resin having an average degree of polymerization of 1000 was obtained.
[시험 예] [Test Example]
상기 실시예 1~8 및 비교예 1~8에서 제조된 염화비닐 수지의 물성을 다음과 같은 방법으로 평가하였다.The physical properties of the vinyl chloride resins prepared in Examples 1 to 8 and Comparative Examples 1 to 8 were evaluated by the following method.
* 수평균 중합도 측정: ASTM D1243-79에 의해 따라 수평균 중합도를 측정하였다.* Number average degree of polymerization: The number average degree of polymerization was measured according to ASTM D1243-79.
*중합시간 측정: 중합 개시제가 투입된 시점부터 반응이 종료될 때까지의 시간을 측정하였다* Polymerization time measurement: The time from when the polymerization initiator was added until the reaction was completed was measured.
*가공 백색도 측정: 제조된 염화비닐계 수지 100중량부에, 복합 안정제(WPS-60, 납계 안정제, 송원산업) 5중량부, 가공조제(PA-822, 아크릴계 가공조제, LG 화학) 1.5중량부, 티타늄 옥사이드 2중량부를 투입하여 180℃에서 3분간 롤-밀을 실시하여 0.5mm 두께의 시트(sheet)를 얻었다.* Processing whiteness measurement: 5 parts by weight of complex stabilizer (WPS-60, lead stabilizer, Songwon Industries), 100 parts by weight of vinyl chloride resin, 1.5 parts by weight of processing aid (PA-822, acrylic processing aid, LG Chemical) 2 parts by weight of titanium oxide was added and roll-milled at 180 ° C. for 3 minutes to obtain a sheet having a thickness of 0.5 mm.
그 후 Nippon Denshoku 사의 NR-3000를 이용하여 백색도 (W.I) 값을 측정하였으며, 그 결과를 표 1 및 2에 정리하였다. 백색도 값으로부터 열 안정성을 측정할 수 있으며, 이 값이 높을수록 열 안정성이 우수한 것으로 판단하였다.Thereafter, the whiteness (W.I) value was measured using Nippon Denshoku's NR-3000, and the results are summarized in Tables 1 and 2. Thermal stability can be measured from the whiteness value, and the higher the value, the better the thermal stability.
* 잔류개시제 농도 측정: 제조된 염화비닐계 수지에 존재하는 잔류 개시제의 함량을 측정하기 위해서 요오드 적정법을 이용하였다. 즉 제조된 수지를 50중량부, 이소프로필 알코올(IPA) 80중량부를 섞은 다음 10% 아세트산 용액 20ml, 10% 포타슘 아이오다이드 용액 20ml를 넣어주고 충분히 혼합하였다.* Residual initiator concentration measurement: Iodine titration was used to measure the content of residual initiator present in the produced vinyl chloride resin. That is, 50 parts by weight of the prepared resin, 80 parts by weight of isopropyl alcohol (IPA) was mixed, and 20 ml of 10% acetic acid solution and 20 ml of 10% potassium iodide solution were mixed and sufficiently mixed.
* 휘시-아이(fish-eye) 수: 염화비닐계 수지 100중량부, DOP 45중량부, 스테아린산 바륨 0.1중량부, 주석계 안정제 0.2중량부, 카본블랙 0.1중량부를 140℃의 6인치 롤을 이용하여 5분간 혼합 혼련한 다음 두께 0.3mm의 시트를 만들고, 이 시트의 400 cm2 중의 백색 투명 입자 수로 나타내었다.* Fish-eye number: 100 parts by weight of vinyl chloride resin, 45 parts by weight of DOP, 0.1 part by weight of barium stearate, 0.2 part by weight of tin stabilizer, and 0.1 part by weight of carbon black using a 6-inch roll at 140 ° C. After mixing and kneading for 5 minutes, a sheet having a thickness of 0.3 mm was formed, and the sheet was expressed as the number of white transparent particles in 400 cm 2 .
*입도 분포 측정: 얻어진 수지를 Sumpatec사의 HELOS 입도 분석기를 이용하여 입경을 측정하고 그때의 스팬(span) 값을 입도 분포로 정의하였다. 이때 스팬 값은 낮을수록 편차가 적음을 의미한다.* Particle size distribution measurement: The obtained resin was measured for particle size using Sumpatec's HELOS particle size analyzer, and the span value at that time was defined as the particle size distribution. In this case, the lower the span value, the smaller the deviation.
표 1
Table 1
구분 | 실시예 1 | 실시예 2 | 실시예 3 | 실시예 4 | 실시예 5 | 실시예 6 | 실시예 7 | 실시예 8 |
승온 속도(℃/min) | 0.2 | 0.4 | 0.6 | 0.05 | 0.2 | 0.2 | 0.2 | 0.2 |
압력저하(△P, kgf/cm2) | 0.1 | 0.1 | 0.1 | 0.1 | 0.05 | 0.15 | 0.1 | 0.1 |
승온시간(분) | 35 | 35 | 35 | 35 | 35 | 35 | 30 | 50 |
중합시간(분) | 264 | 264 | 263 | 267 | 261 | 268 | 260 | 280 |
백색도 | 75 | 75 | 76 | 74 | 75 | 74 | 73 | 76 |
잔류개시제농도(ppm) | 10 | 8 | 5 | 12 | 7 | 11 | 14 | 4 |
휘시아이(개수) | 5 | 5 | 4 | 5 | 4 | 7 | 6 | 6 |
division | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
Temperature rise rate (℃ / min) | 0.2 | 0.4 | 0.6 | 0.05 | 0.2 | 0.2 | 0.2 | 0.2 |
Pressure drop (△ P, kgf / cm 2 ) | 0.1 | 0.1 | 0.1 | 0.1 | 0.05 | 0.15 | 0.1 | 0.1 |
Temperature rise time (minutes) | 35 | 35 | 35 | 35 | 35 | 35 | 30 | 50 |
Polymerization time (minutes) | 264 | 264 | 263 | 267 | 261 | 268 | 260 | 280 |
Whiteness | 75 | 75 | 76 | 74 | 75 | 74 | 73 | 76 |
Residual initiator concentration (ppm) | 10 | 8 | 5 | 12 | 7 | 11 | 14 | 4 |
Whiskey (number) | 5 | 5 | 4 | 5 | 4 | 7 | 6 | 6 |
표 2
TABLE 2
구분 | 비교예1 | 비교예2 | 비교예3 | 비교예4 | 비교예5 | 비교예6 | 비교예7 | 비교예 8 |
승온속도(℃/min) | - | 0.008 | 0.8 | 0.2 | 0.2 | 0.2 | 0.2 | - |
압력저하(△P, kgf/cm2) | - | 0.1 | 0.1 | 0.01 | 0.5 | 0.1 | 0.1 | 0.1 |
승온시간(분) | - | 35 | 35 | 35 | 35 | 10 | 90 | 35 |
중합시간(분) | 260 | 264 | 256 | 253 | 266 | 260 | 349 | 264 |
백색도 | 72 | 72 | 68 | 73 | 72 | 71 | 69 | 74 |
잔류개시제농도(ppm) | 35 | 26 | 2 | 13 | 8 | 29 | 3 | 8 |
휘시아이(개수) | 10 | 11 | 16 | 20 | 23 | 12 | 38 | 15 |
division | Comparative Example 1 | Comparative Example 2 | Comparative Example 3 | Comparative Example 4 | Comparative Example 5 | Comparative Example 6 | Comparative Example 7 | Comparative Example 8 |
Temperature increase rate (℃ / min) | - | 0.008 | 0.8 | 0.2 | 0.2 | 0.2 | 0.2 | - |
Pressure drop (△ P, kgf / cm 2 ) | - | 0.1 | 0.1 | 0.01 | 0.5 | 0.1 | 0.1 | 0.1 |
Temperature rise time (minutes) | - | 35 | 35 | 35 | 35 | 10 | 90 | 35 |
Polymerization time (minutes) | 260 | 264 | 256 | 253 | 266 | 260 | 349 | 264 |
Whiteness | 72 | 72 | 68 | 73 | 72 | 71 | 69 | 74 |
Residual initiator concentration (ppm) | 35 | 26 | 2 | 13 | 8 | 29 | 3 | 8 |
Whiskey (number) | 10 | 11 | 16 | 20 | 23 | 12 | 38 | 15 |
상기 표 1 및 2의 결과로부터 보듯이, 압력 저하가 발생하는 시점에 온도를 승온하여 압력 저하를 방지 하도록 진행한 실시예 1의 백색도 및 휘시아이가 반응 말기 중합 온도를 승온시키지 않은 비교예 1에 비해 향상된 것을 확인할 수 있었다.As can be seen from the results of Tables 1 and 2 above, in the comparative example 1 in which the whiteness and the whiskey of Example 1, which proceeded to raise the temperature at the time when the pressure drop occurred to prevent the pressure drop, did not increase the polymerization temperature at the end of the reaction, It was confirmed that the improvement.
또한 실시예 2 및 3에서와 같이 승온 속도를 조절하여 백색도 및 중합 시간을 조절할 수 있으며 이를 통해 백색도 및 휘시아이를 향상시켰다.In addition, as in Examples 2 and 3, by controlling the temperature increase rate, the whiteness and the polymerization time may be controlled, thereby improving the whiteness and the whiskey.
또한, 압력 저하 시점에 따라 승온 속도를 비교예 2 및 3과 같이 너무 느리게 하거나 빠르게 하였을 때는 휘시 아이 개수의 감소 폭이 상대적으로 적은 것을 확인할 수 있었다.In addition, when the temperature increase rate was too slow or too fast, as in Comparative Examples 2 and 3, the decrease in the number of fish eye was relatively small.
또한 승온 방식이 자켓의 냉각수 유입을 정지시킨 비교예 8에서 보듯이 온도 상승되는 정도가 일정하지 않아 폼 발생을 방지하기 어려워 휘시 아이가 증가한 결과를 볼 수 있었다. In addition, as shown in Comparative Example 8 in which the temperature rising method stopped the inflow of the cooling water of the jacket, the degree of temperature rise was not constant, and it was difficult to prevent foam generation.
따라서, 본 발명에 따르면 압력 저하가 발생하는 반응 말기 시점에 압력 저하 되는 정도에 따라 온도 제어 시스템을 이용하여 중합 온도보다 승온시켜 압력 저하를 방지하였으며 반응 말기 압력 저하와 환류 응축기의 높은 제열량에 의해 발생하는 폼을 억제하여 휘시아이 및 백색도가 높은 염화비닐계 수지를 효율적으로 제조할 수 있었다.Therefore, according to the present invention, the pressure drop was prevented by raising the temperature above the polymerization temperature using a temperature control system according to the degree of pressure drop at the end of the reaction at which the pressure drop occurred, and the pressure drop at the end of the reaction and the high heat removal amount of the reflux condenser By suppressing the foam generated, it was possible to efficiently produce a whiskey and a high vinyl chloride-based resin.
Claims (11)
- 현탁 중합 반응 개시 이후에 반응압력이 0.01 kgf/cm2 초과 내지 0.5 kgf/cm2 미만 저하되는 시점부터, 0.008 ℃/min 초과 내지 0.8 ℃/min 미만의 승온속도로, 10분 초과 내지 90분 미만 동안 승온하는 것을 특징으로 하는From the point of time when the reaction pressure drops from more than 0.01 kgf / cm 2 to less than 0.5 kgf / cm 2 after the start of the suspension polymerization reaction, at a temperature rising rate of more than 0.008 ° C./min to less than 0.8 ° C./min, more than 10 minutes to less than 90 minutes Characterized in that during염화비닐계 수지의 제조방법.Method for producing vinyl chloride resin.
- 제 1항에 있어서,The method of claim 1,상기 저하되는 반응압력은 0.01 kgf/cm2 초과 내지 0.2 kgf/cm2 미만인 것을 특징으로 하는 The decreasing reaction pressure is characterized in that more than 0.01 kgf / cm 2 to less than 0.2 kgf / cm 2염화비닐계 수지의 제조방법.Method for producing vinyl chloride resin.
- 제 1항에 있어서,The method of claim 1,상기 승온속도는 0.008 ℃/min 초과 내지 0.65 미만 ℃/min인 것을 특징으로 하는 The temperature increase rate is characterized in that more than 0.008 ℃ / min to less than 0.65 ℃ / min염화비닐계 수지의 제조방법.Method for producing vinyl chloride resin.
- 제 1항에 있어서,The method of claim 1,상기 승온속도는 온도제어시스템을 조절하는 것을 특징으로 하는The temperature increase rate is characterized in that for adjusting the temperature control system염화비닐계 수지의 제조방법.Method for producing vinyl chloride resin.
- 제 1항에 있어서,The method of claim 1,상기 중합의 반응 온도는 30 내지 80℃ 범위 내인 것을 특징으로 하는 염화비닐계 수지의 제조방법.The reaction temperature of the polymerization is a method for producing a vinyl chloride resin, characterized in that in the range of 30 to 80 ℃.
- 제 1항에 있어서,The method of claim 1,상기 승온 시간은 30 내지 60분인 것을 특징으로 하는 염화비닐계 수지의 제조방법. The temperature increase time is 30 to 60 minutes, characterized in that the vinyl chloride-based resin production method.
- 제 1항 내지 제 6항 중 어느 한 항의 염화비닐계 수지의 제조방법에 의하여 제조됨을 특징으로 하는 Claim 1 to 6 characterized in that it is prepared by the method for producing a vinyl chloride-based resin of any one of염화비닐계 수지.Vinyl chloride resin.
- 제 7항에 있어서,The method of claim 7, wherein상기 염화비닐계 수지는 잔류 개시제 농도가 염화비닐계 수지 100 중량부를 기준으로 0.002 중량부 미만인 것을 특징으로 하는 The vinyl chloride resin is characterized in that the residual initiator concentration is less than 0.002 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.염화비닐계 수지.Vinyl chloride resin.
- 제 7항의 염화비닐계 수지, 무기충진제 및 안정화제를 포함하는 것을 특징으로 하는Claim 7 comprising a vinyl chloride-based resin, inorganic filler and stabilizer염화비닐계 수지 조성물. Vinyl chloride-based resin composition.
- 제 9항에 있어서,The method of claim 9,상기 무기충진제는 카본블랙인 것을 특징으로 하는The inorganic filler is characterized in that the carbon black염화비닐계 수지 조성물. Vinyl chloride-based resin composition.
- 현탁 중합 반응 개시 이후에 반응압력이 0.05 내지 0.1 kgf/cm2 저하되는 시점부터, 0.01 내지 0.5 ℃/min의 승온속도로, 20 내지 60분 동안 승온하는 것을 특징으로 하는From the time when the reaction pressure is lowered from 0.05 to 0.1 kgf / cm 2 after the start of the suspension polymerization reaction, the temperature is increased for 20 to 60 minutes at a temperature increase rate of 0.01 to 0.5 ℃ / min염화비닐계 수지의 제조방법. Method for producing vinyl chloride resin .
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380020181.8A CN104245754B (en) | 2012-12-18 | 2013-10-11 | Suspension polymerization is adopted to prepare the method for vinyl chloride resin |
US14/395,978 US9758604B2 (en) | 2012-12-18 | 2013-10-11 | Method for preparing vinyl chloride-based resin by using suspension polymerization |
IN9081DEN2014 IN2014DN09081A (en) | 2012-12-18 | 2013-10-11 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2012-0148176 | 2012-12-18 | ||
KR20120148176 | 2012-12-18 | ||
KR10-2013-0116248 | 2013-09-30 | ||
KR1020130116248A KR101534399B1 (en) | 2012-12-18 | 2013-09-30 | Method of preapring polyvinyl chloride resin by suspension polymerization |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014098360A1 true WO2014098360A1 (en) | 2014-06-26 |
Family
ID=50978640
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2013/009113 WO2014098360A1 (en) | 2012-12-18 | 2013-10-11 | Method for preparing vinyl chloride-based resin by using suspension polymerization |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2014098360A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000063403A (en) * | 1998-08-21 | 2000-02-29 | Shin Etsu Chem Co Ltd | Preparation of vinyl chloride-based polymer |
KR20080018082A (en) * | 2006-08-22 | 2008-02-27 | 주식회사 엘지화학 | Methods of preparing a vinyl chloride polymer having superior workability |
KR20100040930A (en) * | 2007-07-13 | 2010-04-21 | 가부시키가이샤 구라레 | Process for producing vinyl resin |
KR20120130439A (en) * | 2011-05-23 | 2012-12-03 | 주식회사 엘지화학 | Method of preparing vinyl chloride polymer having excellent polymerization productivity |
KR20120130801A (en) * | 2011-05-24 | 2012-12-04 | 주식회사 엘지화학 | Method of preparing vinyl chloride-based polymers by suspension polymerization |
-
2013
- 2013-10-11 WO PCT/KR2013/009113 patent/WO2014098360A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000063403A (en) * | 1998-08-21 | 2000-02-29 | Shin Etsu Chem Co Ltd | Preparation of vinyl chloride-based polymer |
KR20080018082A (en) * | 2006-08-22 | 2008-02-27 | 주식회사 엘지화학 | Methods of preparing a vinyl chloride polymer having superior workability |
KR20100040930A (en) * | 2007-07-13 | 2010-04-21 | 가부시키가이샤 구라레 | Process for producing vinyl resin |
KR20120130439A (en) * | 2011-05-23 | 2012-12-03 | 주식회사 엘지화학 | Method of preparing vinyl chloride polymer having excellent polymerization productivity |
KR20120130801A (en) * | 2011-05-24 | 2012-12-04 | 주식회사 엘지화학 | Method of preparing vinyl chloride-based polymers by suspension polymerization |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012008654A1 (en) | Production method for a vinyl chloride-based resin having outstanding particle uniformity and heat stability | |
WO2016195434A1 (en) | Method for preparing vinyl chloride-based copolymer and vinyl chloride-based copolymer prepared therefrom | |
WO2016047955A1 (en) | Vinyl chloride-based polymer and method for producing same | |
EP2497787B1 (en) | Vinyl chloride-based polymer | |
WO2016182338A1 (en) | Acryl-based processing aid and vinylchloride-based resin composition containing same | |
WO2014098360A1 (en) | Method for preparing vinyl chloride-based resin by using suspension polymerization | |
US7232867B2 (en) | Process for producing vinyl chloride polymer | |
KR101133962B1 (en) | Method for the preparation of vinyl chloride-based polymer by suspension polymerization | |
KR101534399B1 (en) | Method of preapring polyvinyl chloride resin by suspension polymerization | |
WO2021049836A1 (en) | Method for preparing vinyl chloride-based polymer | |
WO2017104978A1 (en) | Vinyl chloride-based polymer, preparation method therefor, and plastisol containing same | |
WO2017188594A1 (en) | Method for preparing vinyl chloride-based polymer and vinyl chloride-based polymer prepared thereby | |
WO2016047954A1 (en) | Vinyl chloride-based polymer and method for producing same | |
EP3789410B1 (en) | Vinyl chloride polymer and production method thereof | |
WO2017191899A1 (en) | Method for preparing vinyl chloride-based polymer and vinyl chloride-based polymer prepared thereby | |
WO2021256867A1 (en) | Method for producing vinyl chloride-based polymer composite | |
WO2018056604A1 (en) | Method for producing vinyl chloride-based polymer | |
KR101875153B1 (en) | Vinylchloride based resin composition and method for preparing the same | |
WO2019212217A1 (en) | Vinyl chloride polymer and method for preparing same | |
WO2023277530A1 (en) | Method for preparing vinyl chloride-based polymer and vinyl chloride-based polymer prepared thereby | |
KR101529764B1 (en) | Method for preparing vinyl chloride resin and matt, heat deformation resistant vinylchloride resin | |
WO2018056668A1 (en) | Method for preparing vinyl chloride based polymer | |
WO2020060028A1 (en) | Vinyl chloride-based polymer and method for producing same | |
WO2017061829A1 (en) | Vinyl chloride-based polymer and preparation method therefor | |
KR102361955B1 (en) | The method for preparing plasticizer for polyvinyl chloride straight resin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13865298 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14395978 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13865298 Country of ref document: EP Kind code of ref document: A1 |