Oxymethylene polymers, process for the preparation thereof and use thereof
View Patent ↗Oxymethylene polymers having a bimodal distribution or having a distribution of higher modality and having a targeted content of a low molecular weight fraction of from 1 to 5 percent by mass are described. Moldings of these polymers are distinguished by high low-temperature notched impact strength associated with a high modulus of elasticity.
1. An oxymethylene polymer which is a homopolymer or copolymer in which the molar ratio of comonomer units to oxymethylene units is less than 0.008 and which has an at least bimodal molecular weight distribution, wherein the proportion of low molecular weight oxymethylene polymers having molecular weights below 10,000 Dalton is from 1 to 5% by weight, based on the total mass of the oxymethylene polymer the oxymethylene polymer being formed by a process wherein a monomer that forms formaldehyde units is combined optionally together with a comonomer that forms C—C units and together with a chain-transfer agent and a cationic polymerization initiator to form a polymerization mixture in such a way that first a precipitation polymerization is effected homogeneously and, following a period of time the first polymerization is stopped by addition of a basic compound, a temperature profile of the first polymerization being adjusted the period of time being selected so as to stop the first polymerization so that the oxymethylene polymer has a content of low molecular weight constituents of from 1 to 5% by weight.
2. The oxymethylene polymer as claimed in claim 1 , wherein the molar ratio of comonomer units to oxymethylene units is from 0.0004 to 0.005.
3. The oxymethylene polymer as claimed in claim 1 , which has a proportion of terminal alkyl ether groups, based on all terminal groups, of at least 70%.
4. The oxymethylene polymer as claimed in claim 1 , which contains at least 70% of polymers of the general formula
R—O—(CH 2 O) p —(C s H 2s O) q —R′
in which R and R′ are alkyl radicals, s is an integer from 2 to 10 and p and q are averaged random fractions of the comonomers, q/p being less than 0.008.
5. The oxymethylene polymer as claimed in claim 1 , wherein the low molecular weight constituents comprise more than 50 percent by mass of cyclic oxymethylene polymers.
6. The oxymethylene polymer as claimed in claim 1 , wherein the low molecular weight constituents comprise more than 80% by mass of cyclic oxymethylene polymers.
7. The oxymethylene polymer as claimed in claim 1 , wherein the molecular weight distribution of the low molecular weight oxymethylene polymers having molecular weights below 10,000 Dalton has a polydispersity M w /M n of <1.5.
8. The oxymethylene polymer as claimed in claim 1 , wherein the comonomer units are —O—(CH 2 ) 2 —.
9. A molding having good low-temperature notched impact strength comprising the oxymethylene polymer of claim 1 .
10. The oxymethylene polymer as claimed in claim 1 , wherein the molecular weight distribution of the low molecular weight oxymethylene polymers having molecular weights below 10,000 Dalton has a polydispersity of M w /M n of <1.2.
11. The oxymethylene polymer as claimed in claim 1 , wherein the oxymethylene polymer is formed according to a process in which polymerization is stopped by the addition of a basic component to a reaction mixture.
12. The oxymethylene polymer as claimed in clam 1 , wherein the proportion of low molecular weight oxymethylene polymers having molecular weights below 10,000 Dalton is adjusted by time of addition of a basic component to a reaction mixture during formation of the oxymethylene polymer.
13. The oxymethylene polymer as claimed in claim 1 , wherein the proportion of low molecular weight oxymethylene polymers having molecular weights below 10,000 Dalton is adjusted by control of a temperature profile of a reaction mixture during formation of the oxymethylene polymer.
14. The process of claim 1 , wherein the monomer forming formaldehyde units is trioxane.