Mask Material, Melt Blown Nonwovens Special PP Material Can Not Be Bought? Key Raw Material Of Conversion Mask For Petrochemical Enterprises
After the outbreak of the new crown pneumonia, it is urgent to solve the shortage of medical materials such as masks on the market. To this end, many petrochemical enterprises accelerate the breakthrough of technical difficulties and turn to the production of key raw materials for masks.
Sinopec: has successfully butted 11 masks production lines.
It is reported that as of noon on February 7th, Sinopec has completed 11 masks production lines with partners, and is about to enter the installation process. According to preliminary estimates, by February 10th, Sinopec will help to increase the production capacity of new masks by 130 thousand pieces per day. In February 29th, the new capacity will be increased to 600 thousand pieces per day. In March 10th, the new capacity will be increased to 1 million tablets per day.
On the afternoon of February 6th, Sinopec official micro-blog and Yi sent official WeChat issued an article seeking to mask the production cooperation. "I have melted spray cloth, who has a mask machine", got about 8000000 hits, read 25 thousand times, and sent WeChat quickly to 100 thousand +. After the release of micro-blog and WeChat, Mr. Shen's telephone call was quickly explode, and the partners found it within 3 hours.
It is understood that, on the 15 th of this month, there will be 1 masks production lines to take the lead, with 4 on the 20 day and 6 at the end of the month. The Sinopec provides the above equipment to enterprises with production license qualification to expand production and increase production (organize production by leasing the equipment of Sinopec by production enterprises) and provide raw materials for production.
At the same time, Sinopec has also contacted 3 local mask manufacturers, providing them with raw materials and coordinating production equipment. The 1 enterprises in Fangshan District, Beijing, can immediately supply 35 thousand pieces of daily masks; 1 enterprises in Jiangsu, Sinopec, organize raw materials, start commissioning 9 days, produce 100 thousand masks per day, 1 enterprises in Guangdong, Sinopec through coordination, purchase two idle production lines for them, commissioning and commissioning, and can produce more than 100 thousand daily masks. Three enterprises can accumulate more than 235 thousand Nissan masks.
In addition, Sinopec also talks with the central enterprises' emerging China mask manufacturers to provide raw materials for production. On the 16 th of this month, a production line will be trial run to form 100 thousand pieces / Nissan, and 2 production lines will continue to cooperate after the masks are delivered, so as to further improve the production capacity.
Sinopec said that the above production materials were sent to the epidemic areas of Hubei as far as possible, and the need to supply the production enterprises to fight the epidemic and epidemic prevention could also be considered.
Luoyang Petrochemical: high-end non-woven medical materials replacement import
In February 4th, Luoyang Petrochemical Polypropylene warehouse was busy. A 276 ton polypropylene medical material PPH-Y35X sent to Hubei is being organized and exported for downstream customers to produce medical non-woven fabrics.
PPH-Y35X does not contain plasticizer, organic tin, green environmental protection, with high orientation, low ash content, high strength, good spinnability and so on. It fills the blank of the domestic high-end non-woven fabric application field, and is widely used in disposable surgical clothing, absorbable suture, urine diapers, female hygiene products and other products. The product has developed mature production technology, favored by downstream customers, and has broad market prospects. In 2019, Luoyang Petrochemical Company sold 31 thousand and 800 tons of the product, accounting for 24% of the total sales volume of polypropylene.
"The product that the market needs, build Chinese brand, is the idea that my team and I have been adhering to." Cao Yuxin, chief expert of Luoyang petrochemical and chemical technology, has revealed the original intention of developing PPH-Y35X. In recent years, green and low carbon consumption has become the mainstream, and the market demand for PP special materials with high technical content is increasing. Optimizing the product structure, developing special materials and increasing the added value of products become the urgent need to enhance the competitiveness of enterprises.
After conducting market research, they found that domestic non-woven fabrics manufacturers, such as medical, health and chemical separations, used imported raw materials for a long time, and there was no special PP material that could replace imported products in China.
The existing 140 thousand ton / year polypropylene plant in Luoyang petrochemical company adopts advanced domestically produced second generation loop polypropylene technology, creating conditions for developing new products. To speed up the pace of R & D, the company set up a Cao Yuxin expert studio to clarify the division of responsibilities among members, sort out problems and formulate measures. In the trial production process, they used new catalysts to improve the processability and compatibility of polypropylene granules by comparing the performance tests of polypropylene pellets under different catalysts. They analyze the factors that affect the stable production of downstream users during the testing process, and constantly eliminate product defects and improve the quality.
"We have studied the products with other manufacturers of PP special materials." Cao Yu Xin said, "tests show that PPH-Y35X has better physical properties and downstream processing performance than some imported products."
PPH-Y35X is an arduous road to market development after industrial scale production. How to make customers who have used imported materials switch to new domestic materials? Luoyang Petrochemical implements the sales mode of "scientific research personnel + technical personnel + sales personnel", providing users with intimate technical support and services, listening to customers' opinions, and improving the working mechanism of "production, marketing, research and utilization". They also invited users to visit the site to learn about the production management and quality control system of Luoyang Petrochemical Company, so that users can have a clear idea of the company and products.
At present, PPH-Y35X has a good reputation and market in Central China. It meets the quality requirements of similar products of foreign companies. It has passed the environmental health certification of the United States, Japan, Korea and the European Union and other countries and regions, and on behalf of Sinopec unveiled the 2016 fine chemical Europe exhibition and the 2017 Osaka International Rubber and plastic exhibition.
As a key manufacturer of high-end non-woven fabrics, Luoyang Petrochemical has taken the lead in formulating the first domestic polypropylene standard for nonwoven fabrics, and passed the expert evaluation by the National Standards Committee in November 27, 2019.
Yanshan Petrochemical: deep ploughing medical market to meet upgrading needs
In February 8th, Yanshan Petrochemical emergency production of 2500 tons of medical syringe special material polypropylene (PP) K4912 factory, next, they will continue to produce 300 tons of medical syringe special material polypropylene K4925, to ensure the supply of high-quality medical materials. Recently, the company has formulated a contingency plan for production, supply and marketing, giving priority to the production of medical grade polypropylene and providing raw materials for downstream enterprises.
At present, Yanshan Petrochemical has 3 polypropylene units, with an annual capacity of 500 thousand tons, which can produce raw materials including transfusion containers, syringes and other medical supplies.
●?? Deepening the field of medical polypropylene segmentation
With the development of economy and the improvement of medical standard, the market of medicine, medical supplies and equipment has expanded rapidly. According to the data of the National Bureau of statistics, the market turnover in 2018 was 151 billion 800 million yuan, and the average annual growth rate in 2015~2018 was 19%. In the meantime, medical plastics have also been developing rapidly. With the rapid development of science and technology, the scope of application has been expanding.
Polyolefin is one of the most widely used medical plastics. Polypropylene is widely used in medical catheters, infusion containers, packaging materials, syringes and other fields, and has obvious advantages. For example, polypropylene infusion bottle (bag) has the advantages of good chemical stability, no drop off, light weight and good impact resistance. Compared with glass infusion bottles, it is more suitable for long-term storage and easy transportation.
Yanshan Petrochemical has grasped the development trend of high-end and differentiated products and is at the forefront of the development and production of medical polypropylene in China. Since the first successful development of medical grade 1304 and B205 products in the 80s and 90s of last century, the company has gradually developed and produced polypropylene medical infusion packaging materials B4902 and B4908, high penetration polypropylene K4912 and K4912R for syringe, and high grade mobile polypropylene K4818, K4925, three yuan copolymerization polypropylene F5606Y, F5806Y and other medical grade products. These products are widely used in the production of medical consumables, such as infusion bottles, infusion bags, syringes and medicine bottles.
In 2019, the annual output of Yanshan petrochemical material was nearly 30 thousand tons, and the output in 2020 was estimated to be about 40 thousand tons.
● Ten years grinding out special infusion material
Behind the successful entry into the medical market is Yanshan Petrochemical's efforts in the past more than 10 years. Taking infusion bottles (bags) as an example, since 1980s, developed countries have gradually adopted polypropylene instead of glass for transfusion packaging. Domestic infusion packaging manufacturers in recent years also widely used plastic, glass bottle figure gradually difficult to find. According to a survey paper published in 2013 on rational drug use in China, the largest number of plastic bottles was used in different packaging forms in China (55.03%), followed by soft plastic bags (40.19%) and glass bottles (4.78%). Plastic packaging quickly replaced glass, but before 2015, the raw materials of these packages depended on imports for a long time. A large infusion is a liquid sterilization preparation with a volume of not less than 50 milliliters and directly injected into the body by intravenous drip.
Medical materials have many advantages, such as high certification, high threshold, high price and small output. Yanshan Petrochemical has listed the development and popularization of medical polyolefin products as a key research project. Production technicians have repeatedly visited the domestic infusion clients to provide product testing and keep track of the test, and actively communicate with the national authoritative experts for details. Ten years of grinding, in November 2017, the company's polypropylene products successfully completed the injection, blowing, filling and filling test at the leading pharmaceutical company, Sichuan colon group. The test product was formed at one time, and the target 100% met the production inspection standard.
Yanshan Petrochemical Polypropylene B4908 and B4902 series products for large infusion development. The series products have different melt mass flow rate (MFR), which can meet the demand of various process routes for transfusion packaging. The product meets the requirements of pharmacological examination, is safe, non-toxic and suitable for long-term storage. With the increase of storage time, the number of microparticles in the liquid does not change, and it will not have adverse effects on the human body. The product also has the advantages of good heat resistance, high transparency, good fluidity and high rigidity.
● Through the State Food and Drug Administration related Reviews
In February 12, 2018, Yanshan Petrochemical Polypropylene B4908 and B4902 products broke through the long-term dependence on imports of medical polypropylene infusion packaging materials through the safety certification of the national authority. This means that Sinopec medical polypropylene once again crossed the threshold of the market.
It is only the first step to pass the national authority's safety certification. Medical packaging contact drugs directly enter the patient's blood. Therefore, the products have high access threshold, strict inspection standards, long inspection cycle and difficult evaluation. According to the state regulations, pharmaceutical companies must synchronously activate the registration number of pharmaceutical packaging materials (drug packaging materials) when they apply for drug approval before they can be used in compliance. That is to say, drug packages and drugs should be approved by association at the same time before entering the market.
In September 2019, Shijiazhuang four drugs Co., Ltd. adopted the vertical infusion bag produced by Yanshan Petrochemical special polypropylene compound B4902, and Sodium Chloride Injection, which was packaged with it, passed the related evaluation of the State Drug Administration. This means that the four drug companies can legitimately make use of this special material instead of import. Yanshan Petrochemical Polypropylene B4902 has become the first polypropylene packaging material for transfusion through related reviews after China's new drug trial system reform. Sinopec medical polypropylene special material has been gradually recognized by customers and opened the market of pharmaceutical packaging materials.
Baling Petrochemical: continuous breakthrough in medical SEBS
Recently, the "national biomaterials production and application demonstration platform construction" start meeting and implementation plan evaluation will be held in Xinxiang, Henan. The construction of 10000 tons of medical SEBS industrial equipment in Baling Petrochemical Project will be included in the national new material production and application demonstration platform project.
SEBS is a new generation of high performance styrene type thermoplastic elastomer. It has the characteristics of aging resistance, safety, innocuity, and environmental protection. It is mainly used in pharmaceutical packaging, medical infusion equipment, food packaging, etc., and it is a key development product of national strategic emerging industries. Baling Petrochemical took the lead in adopting independent intellectual property technology in 2006 to realize SEBS industrial production. The company now has capacity of over 40 thousand tons in SEBS, and has been approved to build a similar device with an annual output of 50 thousand tons.
With the continuous improvement of people's living standards and national environmental protection requirements, SEBS with superior performance is widely recognized as an excellent substitute for PVC. As a replacement material for medical transfusion tube materials, there is a huge demand for medical SEBS every year. Before 2016, medical SEBS production technology was monopolized by us and Japanese companies, which seriously affected the development of related industries in China.
In 2007, Baling Petrochemical began to carry out research on new medical SEBS varieties and developed two new brand products. In May 2009, medical SEBS trial products were successfully produced. In 2010, the company cooperated with the leading company of China's medical device industry, Wei Gao group, to carry out medical SEBS research and development. The product has passed the testing of USP VI medical plastics, and can be used in three kinds of medical devices (the three class medical devices are the highest level). When using Balin petrochemical SEBS to produce transfusion tube, no plasticizer is needed, so that the harm of soft PVC infusion pipe containing DEHP (two phthalate) plasticizer to human body is avoided.
In the first half of 2016, Baling Petrochemical SEBS entered the stage of industrial mass production, successfully breaking the monopoly of foreign countries and filling the gap in China. In the same year, Sinopec and Wei Gao signed a strategic cooperation agreement, focusing on the strategic planning of China's high-end and high-quality medical consumables, and jointly developing new materials with high added value and high performance to achieve the localization of high-end and high quality medical consumables.
In 2017, the development and industrialization of styrene polymer thermoplastic elastomers and polycaprolactone medical polymer raw materials declared by Wei Gao group was selected as the key research and development plan of the national key research and development plan "Bio Medical Materials Research and development and tissue and organ replacement". Baling Petrochemical, as a member of the project, works with the Wei Gao group to carry out the project research and development. In early 2018, Baling Petrochemical was responsible for the scientific and technological breakthrough in Hunan's strategic emerging industries, namely, "non polyvinyl chloride medical polymer materials (SEBS) technology", which was accepted by the Hunan provincial science and technology department.
In December 2019, the "ten dragons" project of Sinopec's science and technology tackled by Baling Petrochemical took the lead in the development and application of polymer materials for medical consumables. During the tackling period, the project team successfully developed 11 brand names for medical consumables. The products were applied through relevant medical tests and applied in the downstream enterprises such as the Wei Gao group. The total production and sales volume was nearly 80 thousand tons, and 10 Chinese invention patents were applied, 4 of which were authorized.
The successful development of polymer materials for medical consumables in China has broken the monopoly position of imported products. It has played a positive role in alleviating the contradiction between supply and demand of raw materials for the upgrading of medical materials industry in China, and reducing the material cost of universal medical care. It also provided a successful case for Sinopec's foundation in the field of materials and high-end strategy.
Common medical polymer materials
There are nearly 100 kinds of polymer materials used in medical plastic products, including PVC, PE, polypropylene (PP), polytetrafluoroethylene (PTFE), thermoplastic polyurethane (TPU), polycarbonate (PC) and polyester (PET). Besides common masks, isolating clothes, syringes, infusion bags, masks, goggles and gloves, it is also used for artificial organs.
● Polyethylene (PE)
PE is a milky, tasteless, odorless and non-toxic glossy waxy granule. It is cheap and has better performance, including low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and ultra high molecular weight polyethylene (UHDPE).
HDPE has fewer branched chains, relatively high molecular weight, high crystallinity and density, high hardness and strength, poor transparency and high melting point. It is mainly used for packaging, such as medicine bottles, medical caps, etc. HDPE has good mechanical properties and has been applied in artificial organs, such as artificial lung, artificial trachea, artificial kidney, artificial urethra and so on, and has been applied in surgical repair materials.
LDPE has many branched chains, so its molecular weight is relatively small, its crystallinity and density are low. It has good softness, impact resistance and transparency. It is commonly used in blown film. It is one of the alternatives to PVC. It is mainly blended with other materials to produce medical packaging bags, intravenous injectors and so on. According to the performance requirements, HDPE and LDPE two materials can be mixed.
UHDPE has high impact strength, low friction, stress cracking resistance and good energy absorption characteristics, making it an ideal material for artificial knees and shoulder connectors.
●? Polypropylene (PP)
PP is colorless, tasteless, non-toxic and looks similar to polyethylene, but it is more transparent and lighter than polyethylene. It has the advantages of innocuity, easy processing, impact resistance and flexural resistance. Medical PP has high transparency, good barrier and radiation resistance. It is widely used in medical supplies and packaging such as syringes, respirators and so on.
Take the respirator as an example, medical masks are mainly made of non-woven fabrics made of PP. Nonwoven fabrics are spunbonded nonwovens (melt index of raw materials 30~40) and melt blown nonwovens (material melt index is above 500). Medical masks are usually 3 layers of SMS. SMS is spunbonded layer (Spunbond), melt blown layer (Meltdown) and spunbond layer (Spunbond) respectively.
The diameter of spunbond fiber is relatively thick, about 20 microns. The main function of the two layer spunbond layer is to support the whole non-woven fabric structure, which has little effect on the barrier. Melt blown layer is the main factor affecting the filtration efficiency and product price. The diameter of the fiber is about 2 microns. Only the 1/10 of the spunbond layer plays an important role in preventing bacteria and blood permeating mask. Researchers are also developing more finer fibers to enhance antimicrobial barrier properties.
●? Polyvinyl chloride (PVC)
Pure PVC is atactic, hard and brittle, and rarely used. Producers can add different additives to achieve the required physical and mechanical properties. With the addition of suitable plasticizer in PVC, transparent products with different hardness and hardness can be made.
Hard PVC does not contain or contain a small amount of plasticizers. It has good tensile, bending, compressive and impact resistance properties. It can be used as structural material alone. Soft PVC contains more plasticizers, softness, elongation at break and cold resistance increase, but brittleness, hardness and tensile strength decrease.
PVC is widely used in medical plastics, mainly because of its low cost and easy processing. The common products are hose, respirator and so on. But manufacturers are also seeking alternatives because plasticizers are increasingly demanding.
● Polycarbonate (PC)
The typical characteristics of PC are toughness, strength, rigidity and steam sterilization. These characteristics make PC preferentially be used as raw material for hemodialysis filters, surgical tools and oxygen tanks (which can remove carbon dioxide and increase oxygen in the blood during surgical heart surgery). The application of PC also includes needle free injection system, infusion apparatus, piston and so on.
●? Styrene butadiene styrene block copolymer (SEBS)
SEBS has good elasticity, elongation at break, small permanent deformation, high transparency, good thermal stability, steam and ethylene oxide and UV disinfection, non-toxic, easy to process and so on. It can make disposable infusion sets, sealing aprons for disposable syringes, and blood bags, infusion caps, tourniquet and so on.
SEBS is often used in combination with other components. According to the requirements of different application fields, various kinds of blends can be made by mixing many substances in SEBS, such as oil, other polymers, filling materials and additives (antioxidants, pigments).
The addition of filler oil can increase the fluidity of SEBS, improve its processability, adjust the hardness of the blend, and reduce the cost. The organic solution of SEBS oil blend can replace natural latex to manufacture surgical gloves and other products. Because SEBS does not contain unsaturated double bonds and has high purity, the medical and health products made have two advantages: first, the antioxidant and ozone resistance are better; two, natural latex contains protein, which may lead to allergies in some patients, while SEBS does not.
● Acrylonitrile butadiene styrene copolymer (ABS)
ABS has a certain degree of rigidity, hardness, impact resistance and chemical resistance, radiation resistance and ethylene oxide disinfection. ABS is mainly used for surgical instruments, roller clips, plastic needles, tool boxes, diagnostic devices and hearing aids, especially for large medical equipment.
●? Polytetrafluoroethylene (PTFE)
Polytetrafluoroethylene resin is a white opaque waxy powder. It has excellent high temperature resistance, low temperature resistance, chemical corrosion resistance, moisture resistance and abrasion resistance. It is nontoxic, biocompatible and lubricated. Its friction coefficient is very low. It is only polyethylene 1/5.
Based on these excellent properties, PTFE can be directly implanted into the body, used for artificial blood vessels and rhinoplasty. Besides, it can also be used in functional components of biochemical analysis and biochemical synthesis equipment, such as cell and tissue culture device.
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