KR0160332B1 - Processing method of high porous vinyl chloride resin - Google Patents
Processing method of high porous vinyl chloride resin Download PDFInfo
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- KR0160332B1 KR0160332B1 KR1019940029842A KR19940029842A KR0160332B1 KR 0160332 B1 KR0160332 B1 KR 0160332B1 KR 1019940029842 A KR1019940029842 A KR 1019940029842A KR 19940029842 A KR19940029842 A KR 19940029842A KR 0160332 B1 KR0160332 B1 KR 0160332B1
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- 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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Abstract
본 발명은 다공성 염화비닐 수지의 제조방법에 관한 것으로서, 좀더 상세하게는 염화비닐 수지의 현탁중합시 중합 초기 온도를 중합 말기의 온도보다 낮추어 중합을 진행시키다가 일정 중합전화율에 도달하면 중합 말기의 온도로 상승시켜 중합을 실시하는 것을 특징으로 하는 염화비닐 수지의 품질, 특히 염화비닐 수지의 다공성(Porosity)을 증가시키는 염화비닐 수지의 현탁 중합 방법에 관한 것이다.The present invention relates to a method for preparing a porous vinyl chloride resin, and more particularly, in the case of suspension polymerization of vinyl chloride resin, the polymerization temperature is lowered below the temperature at the end of the polymerization, and the polymerization proceeds when the polymerization conversion rate is reached. It relates to a suspension polymerization method of vinyl chloride resin to increase the quality of the vinyl chloride resin, in particular, the porosity of the vinyl chloride resin, characterized in that the polymerization is carried out by raising.
염화비닐 수지의 다공성이 증가될 경우, 가공제품에 많은 양의 첨가제들이 흡수될 수 있어 생산성과 제품의 품질을 향상시킬수 있다.When the porosity of vinyl chloride resin is increased, a large amount of additives can be absorbed in the processed product, thereby improving productivity and product quality.
Description
본 발명은 다공성 염화비닐 수지의 제조방법에 관한 것으로서, 좀 더 상세하게는 염화비닐 수지의 현탁 중합 방법을 개선하여 염화비닐 수지의 품질, 특히 염화비닐 수지의 다공성(Porosity)을 증가시키는 염화비닐 수지의 현탁 중합방법에 관한 것이다. 염화비닐 수지의 다공성이 증가될 경우, 가공 제품에 많은 양의 첨가제들이 균일하게 흡수될 수 있어, 생산성과 제품의 품질을 향상시킬수 있다.The present invention relates to a method for producing a porous vinyl chloride resin, and more particularly, to improve the suspension polymerization method of vinyl chloride resin, vinyl chloride resin to increase the quality of vinyl chloride resin, in particular, the porosity of vinyl chloride resin. It relates to a suspension polymerization method of. When the porosity of vinyl chloride resin is increased, a large amount of additives can be uniformly absorbed in the processed product, thereby improving productivity and product quality.
종래에는 염화비닐 수지의 다공성을 개선시키기 위하여 현탁제인 부분검화 폴리비닐 알코올의 검화도의 변경, 현탁중합기의 교반속도와 교반기의 형태변경, 비이온계유화제의 사용등 여러 가지 방법들이 사용되었다. 이러한 방법들은 각각 장단점이 있는데, 예를 들면 비이온계 유화제를 사용하는 경우에는 염화비닐 수지의 다공성을 현저히 개선시킬수 있는 장점이 있는 반면, 염화비닐 수지의 열안정성이 저하되어 염화비닐 수지의 가공시 열안정제 선택에 상당한 주의를 요하는 문제점이 있다.Conventionally, in order to improve the porosity of vinyl chloride resin, various methods such as changing the degree of saponification of a partially saponified polyvinyl alcohol as a suspending agent, changing the stirring speed and the shape of the stirrer, and using a nonionic emulsifier have been used. Each of these methods has advantages and disadvantages. For example, when a nonionic emulsifier is used, the porosity of the vinyl chloride resin can be significantly improved, while the thermal stability of the vinyl chloride resin is lowered. There is a problem that requires considerable attention in the selection of heat stabilizers.
다공성을 증가시키기 위한 염화비닐 수지의 현탁중합 방법에 관하여 상세히 설명하기에 앞서, 우선적으로 염화비닐 수지의 입자 생성 과정을 간략히 설명하면 다음과 같다.Prior to describing in detail the suspension polymerization method of the vinyl chloride resin to increase the porosity, a brief description of the particle generation process of the vinyl chloride resin is as follows.
염화비닐 수지의 입자 생성과정은 교반력에 의하여 염화비닐 단량체(VCM)액적이 생성되며, 생성된 염화비닐 단량체 액적이 현탁제에 의하여 액적의 이합집산이 조절되어 최종 염화비닐 수지 입자가 형성된다. 염화비닐 모노머 액적내에 존재하는 개시제의 라디칼(Radical)이 염화비닐 단량체와 반응을 하여 염화비닐 수지의 일차 입자(Primary Particle)가 형성되고, 형성된 일차 입자간의 응집에 의하여 어그로머레이트(Agglomerate)가 형성되며, 전화율이 70%에 도달하면 염화비닐 단량체와 염화비닐 수지의 밀도차에 의하여 수축 현상이 일어나게 되어 가공이 형성되게 된다.In the particle generation process of the vinyl chloride resin, vinyl chloride monomer (VCM) droplets are generated by the stirring force, and the resulting vinyl chloride monomer droplets are controlled by dimerization of the droplets by a suspending agent to form final vinyl chloride resin particles. The radical of the initiator present in the vinyl chloride monomer droplet reacts with the vinyl chloride monomer to form primary particles of the vinyl chloride resin, and agglomerate is formed by aggregation between the formed primary particles. When the conversion rate reaches 70%, shrinkage occurs due to the density difference between the vinyl chloride monomer and the vinyl chloride resin, thereby forming processing.
염화비닐 수지의 현탁 중합에서 다공성이 향상되는 메카니즘(Mechanism)은 다음 두가지로 요약될 수 있는데,Mechanism that improves porosity in suspension polymerization of vinyl chloride resin can be summarized as following.
첫째, 염화비닐 단량체 액적의 계면장력을 낮춤으로써 중합되고 있는 액적의 수축력을 감소시켜 다공성을 향상시키는 방법과,First, by reducing the interfacial tension of the vinyl chloride monomer droplets to reduce the shrinkage of the polymerized droplets to improve porosity,
둘째, 염화비닐 단량체에 현탁제가 액적안에서 형성되는 염화비닐 수지의 일타입자의 콜로이드(Colloid)안정성을 변화시킴으로써 다공성을 개선시키는 방법이 있다.Second, there is a method of improving porosity by changing the colloidal stability of the single particles of the vinyl chloride resin in which the suspending agent is formed in the droplets of the vinyl chloride monomer.
따라서 본 발명자들은 염화비닐 수지의 현탁 중합 과정에서 염화비닐 수지의 입자 생성과정을 예의 주시하여 염화비닐 수지의 다공성을 향상시킬 수 있는 방법을 연구한 결과, 본 발명을 완성하게 되었다.Accordingly, the present inventors have carefully studied the method of improving the porosity of the vinyl chloride resin by closely monitoring the particle formation process of the vinyl chloride resin in the suspension polymerization process of the vinyl chloride resin, and thus, the present invention has been completed.
즉, 본 발명은 염화비닐 또는 염화비닐 공중합 제조시 중합 진행의 초기단계에서 염화비닐 단량체의 액적에 녹아 있는 개시제가 라디칼로 분해되어 염화비닐 단량체가 염화비닐 단량체의 액적에 녹아 있는 개시제가 라디칼로 분해되어 염화비닐 단량체가 염화비닐 수지로 중합되는 과정에서 생성되는 일차 입자의 수를 증가시킴으로써 염화비닐 수지의 다공성을 향상시키는 다공성 염화비닐 수지의 제조방법을 제공하는데 그 목적이 있다.That is, in the present invention, in the preparation of vinyl chloride or vinyl chloride copolymerization, the initiator dissolved in the droplets of the vinyl chloride monomer is decomposed into radicals at the initial stage of the polymerization process, and the initiator in which the vinyl chloride monomer is dissolved in the droplets of the vinyl chloride monomer is decomposed into radicals. It is an object of the present invention to provide a method for producing a porous vinyl chloride resin to improve the porosity of the vinyl chloride resin by increasing the number of primary particles generated during the polymerization of the vinyl chloride monomer to the vinyl chloride resin.
본 발명을 좀더 상세히 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명의 염화비닐 수지의 제조방법은 염화비닐 수지의 현탁 중합시 현탁제인 부분검화 폴리비닐알콜의 검화도와 중합도를 적절히 선정하고, 중합 초기의 온도를 중합 말기의 온도와 비교하여 10 내지 30℃, 더 상세하게는 10 내지 20℃낮추어 중합을 실시하다가, 중합전화율이 0.1%에서 30%, 더 상세하게는 0.5%에서 25%까지 진행되면, 중합온도를 중합말기의 온도로 상승시키면서 중합을 진행시키는 방법으로 이루어져 있다. 이때 중합전화율이 0.1%미만에서는 염화비닐단량체 액적내의 폴리염화비닐의 일차 입자가 균일한 상태로 얻어질수 없으므로 다공성이 향상되지 않으며, 중합전화율이 30%를 초과하면 다공성은 향상되지만 중합시간이 지나치게 길어짐으로써 중합생산성이 저해되는 단점이 있다.In the method for producing a vinyl chloride resin of the present invention, the saponification degree and degree of polymerization of a partially saponified polyvinyl alcohol as a suspending agent during suspension polymerization of a vinyl chloride resin are appropriately selected, and the temperature of the initial polymerization is 10 to 30 ° C, More specifically, the polymerization is carried out by lowering the temperature from 10 to 20 ° C., and when the polymerization conversion rate is 0.1% to 30%, more specifically 0.5% to 25%, the polymerization is carried out while raising the polymerization temperature to the temperature at the end of the polymerization. Consists of ways. At this time, if the polymerization conversion rate is less than 0.1%, the primary particles of polyvinyl chloride in the vinyl chloride monomer droplets cannot be obtained in a uniform state, and the porosity is not improved. As a result, polymerization productivity is impaired.
상기 중합방법을 이용하여 염화비닐 단량체 또는 염화비닐 단량체와의 공중합으로 얻은 단량체와의 혼합물을 현탁 중합하는 경우, 전술한 바와 같이 염화비닐 수지의 다공성이 향상되고, 환류 옹축기를 부설한 중합기를 이용할 경우에는 더욱 현저한 효과를 얻을 수 있게 된다.In the case of suspension polymerization of a vinyl chloride monomer or a mixture with a monomer obtained by copolymerization with a vinyl chloride monomer using the polymerization method, as described above, the porosity of the vinyl chloride resin is improved and a polymerization reactor having a reflux condenser is used. In this case, a more remarkable effect can be obtained.
본 발명에서 염화비닐 단량체와의 공중합으로 얻은 단량체로서는 예를 들면 에틸렌, 프로필렌 등의 올레핀류, 초산비닐, 스테아린산 비닐 등의 비닐 에스테르류, 아크릴산 메틸, 메타아크릴산 메틸등의 아크릴산 에스테르류, 말레인산 또는 후말산등의 산의 에스테르류 또는 무수물, 아크릴로니트릴 등의 니트릴 화합물 혹은 염화비닐리덴과 같은 비닐리덴 화합물들이 있다.Examples of the monomer obtained by copolymerization with a vinyl chloride monomer include olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl stearate, acrylic esters such as methyl acrylate and methyl methacrylate, maleic acid or Esters of acids such as malic acid or anhydrides, nitrile compounds such as acrylonitrile or vinylidene compounds such as vinylidene chloride.
본 발명에 사용되는 중합개시제로는 염화비닐 현탁중합에서 통상적으로 사용되고 있는 개시제, 예를 들면 라우로일 퍼옥사이드, 3,5,5-트리메틸헥실 퍼옥사이드, t-부틸퍼옥시피발레이트, t-부틸퍼옥시네오디카보네이트, 디이소프로필퍼옥시디카보네이트, 디-2-에틸헥산퍼옥시네오디카보네이트 또는 아세틸 사이크로헥실스포닐퍼옥사이드 등과 같은 유기 과산화물 또는 α,α'-아조비스이소 부틸로니트릴 또는 α,α'-아조비스 2,4-메틸파레로니트닐 등의 아조화합물의 1종 또는 2종 이상의 혼합물이 사용되고 있다.As polymerization initiators used in the present invention, initiators commonly used in vinyl chloride suspension polymerization, for example, lauroyl peroxide, 3,5,5-trimethylhexyl peroxide, t-butylperoxy pivalate, t- Organic peroxides such as butyl peroxy neodicarbonate, diisopropyl peroxy dicarbonate, di-2-ethylhexaneperoxy neodicarbonate or acetyl cyclohexyl phosphonyl peroxide or α, α'-azobisisobutylonitrile or One kind or a mixture of two or more kinds of azo compounds such as α, α'-azobis 2,4-methylpareronitryl are used.
본 발명에서 사용되는 현탁제로는 공지의 현탁제, 예를 들면 부분 검화 폴리비닐알콜, 초산비닐무수말레인산 공중합체, 폴리비닐피로리돈, 젤라틴, 메틸셀루로우즈, 하이드록시 프로필셀루로우즈, 하이드록시 에틸셀루로우즈 등이 사용된다. 상기 현탁제는 폴리비닐 알콜의 검화도가 70에서 90%인 1차 현탁제와 검화도가 30에서 50%인 2차 현탁제을 혼용하여 사용할 수있다.Suspending agents used in the present invention include known suspending agents, such as partially saponified polyvinyl alcohol, vinyl acetate maleic anhydride copolymer, polyvinylpyrrolidone, gelatin, methylcellulose, hydroxy propylcellulose, and hydroxy. Ethyl cellulose and the like are used. The suspending agent may be used in combination with a primary suspending agent having a saponification degree of 70 to 90% of polyvinyl alcohol and a secondary suspending agent having a saponification degree of 30 to 50%.
본 발명에 따르면 필요에 따라 분자량 조절제를 사용하는 것도 가능하다.According to the present invention, it is also possible to use a molecular weight regulator as necessary.
또한, 중합반응에 사용되는 개시제, 현탁제, 분자량 조절제 등은 최초에 일관적으로 중합반응계에 첨가하거나, 중합반응중 분할하여 첨가하는 것도 가능하다.In addition, an initiator, a suspending agent, a molecular weight regulator, etc. used for a polymerization reaction can be added to a polymerization reaction system consistently at the beginning, or can be added separately in a polymerization reaction.
본 발명에 따르면 중합반응의 온도범위는 통상40∼75℃가 가능하지만, 특히 여기에 한정되는 것은 아니다.According to the present invention, the temperature range of the polymerization reaction can usually be 40 to 75 ℃, but is not particularly limited thereto.
[실시예1∼4, 비교예1][Examples 1 to 4 and Comparative Example 1]
직경 0.6m이며, 체적 0.28㎥인 브루마진 교반기가 장착된 중합기를 사용하여 하기 표1에 기재된 중합처방을 근거로 시험중합을 실시하였다. 중합온도는 58℃이며, 표1에 나타난 중합조건의 초기 온도와 시간에 따라 중합을 진행하였다. 중합기의 중합압력이 반응압의 0.5kg/㎠저하될 때 미반응 단량체를 회수하고 염화비닐 수지를 얻는다. 이때의 중합전화율은 78%이었다. 비교하기 위하여 통상의 중합조건을 비교예1에 나타내었다. 얻어진 염화비닐 수지는 하기의 방법에 따라 물성을 평가하였으며, 얻어진 결과를 하기 표2에 나타내었다. 표1에서 보는 바와 같이 통상의 가소제 흡수속도와 다공성이 현저히 향상됨을 알 수 있다.The test polymerization was carried out based on the polymerization prescription shown in Table 1 below using a polymerization reactor equipped with a bromazine stirrer having a diameter of 0.6 m and a volume of 0.28 m 3. The polymerization temperature was 58 ℃, the polymerization proceeded according to the initial temperature and time of the polymerization conditions shown in Table 1. When the polymerization pressure of the polymerization reactor decreases by 0.5 kg / cm 2 of the reaction pressure, the unreacted monomer is recovered and a vinyl chloride resin is obtained. The polymerization conversion rate at this time was 78%. Conventional polymerization conditions are shown in Comparative Example 1 for comparison. The obtained vinyl chloride resin was evaluated for physical properties according to the following method, and the results obtained are shown in Table 2 below. As shown in Table 1 it can be seen that the conventional plasticizer absorption rate and porosity is significantly improved.
[물성평가방법][Property evaluation method]
① 겉비중 : KS M3002에 따름.① Overweight: According to KS M3002.
② 입도분포 : 쉬이브(Sieve)법에 따름.② Particle size distribution: According to the Sieve method.
③ 가소제 흡수속도 : 염화비닐수지 400g을 브라벤더(Brabender)의 플레니터리 믹서(Planetary Mixer)에 넣고 90℃에서 5분동안 교반시킨 후 가소제인 DOP(Dioctyl phthalate)를 200g 투입하면서 토오크(Torque)변화에 따른 가소제 흡수시간을 관찰한다(ASTM D2396).③ Plasticizer Absorption Rate: Put 400g of vinyl chloride resin into Planetary Mixer of Brabender and stir at 90 ℃ for 5 minutes, and then add 200g of plasticizer DOP (Dioctyl phthalate) to Torque. Observe the plasticizer absorption time according to the change (ASTM D2396).
④다공성(Porosity) : 이태리 Carlo Erba사제의 수은 가압식 포로시메타(PO-2000)를 이용하고, 절대압31∼1011psi(공경 0.17∼5.8㎛)사이의 염화비닐수지 100g당 사입된 수은의 용량을 측정하여 다공성을 측정한다.④ Porosity: Using a mercury pressurized porosimeter (PO-2000) manufactured by Carlo Erba, Italy, the capacity of mercury injected per 100 g of vinyl chloride resin between 31 to 1111 psi (0.17 to 5.8 μm in diameter) was measured. Measure porosity by
[실시예5∼7,비교예2][Examples 5 to 7 and Comparative Example 2]
전열면적 0.4㎡의 환류응축기를 부설한 내경 0.286m의 40L, 중합기에서 하기 표1에 나타낸 중합처방과 중합조건을 변경하면서 시험중합을 실시하였다. 환류응축기의 사용시기는 통상의 조건에 따르며, 중합전화율이 5%가 되는 시점에서 환류응축기에 냉각수를 통과 개시하고, 통수 개시후 30분 이내에 환류응축기에서의 제열량 400kcal/hr가 되도록 조절하여 중합을 유지하고 중합기내의 압력이 반응압보다 0.5kg/㎠저하될 때 환류응축기의 운전을 정지하고 미반응 단량체를 회수하여 염화비닐 수지를 얻는다. 이때의 중합전화율은 78%이다. 초기의 중합온도45℃에서 표1에 나타난 실시예5∼7에 따라 중합시간을 변경하면서 시험중합을 실시하였다. 비교예2로써 통상의 환류응축기 사용조건에서 시험중합을 시행하였다. 얻어진 수지의 평가결과는 하기 표2에서 알수 있는 바와 같이, 통상의 중합조건에서 생성된 염화비닐 수지에 비하여 가소제 흡수속도가 빠르고 다공성이 큰 값을 나타내었으며, 환류응축기를 사용하지 않는 통상의 중합처방에 의하여 생산된 염화비닐수지(비교예1)과 비교하면 동들이상의 수준으로 얻어졌다.The test polymerization was carried out in a 40L, polymerizer having an inner diameter of 0.286 m and a polymerization reactor in which a reflux condenser having a heat transfer area of 0.4 m2 was installed while changing the polymerization prescription and polymerization conditions shown in Table 1 below. The use time of the reflux condenser is in accordance with the usual conditions, and when the polymerization conversion rate is 5%, it starts to pass through the cooling water to the reflux condenser, and the polymerization is controlled to be 400 kcal / hr of the heat removal in the reflux condenser within 30 minutes after the start of water flow. When the pressure in the polymerization reactor is 0.5kg / ㎠ lower than the reaction pressure, the reflux condenser is stopped and the unreacted monomer is recovered to obtain a vinyl chloride resin. The polymerization conversion rate at this time is 78%. Test polymerization was carried out at varying polymerization times in accordance with Examples 5 to 7 shown in Table 1 at the initial polymerization temperature of 45 ℃. As Comparative Example 2, test polymerization was performed under normal reflux condenser use. As can be seen in Table 2 below, the result of the evaluation of the obtained resin showed a higher plasticizer absorption rate and a higher porosity than the vinyl chloride resin produced under the conventional polymerization conditions, and showed a general polymerization prescription without using a reflux condenser. Compared with the vinyl chloride resin produced in Comparative Example 1, copper was obtained at the level of phase.
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